Note: Descriptions are shown in the official language in which they were submitted.
2 1 78037
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Case No. 271 IR-01
A COMPOSITION FOR PROVIDING ANTI-SHUDDER FRICTION
DURABILITY PERFORMANCE FOR AUTOMATIC TRANSMISSIONS
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention encompasses compositions for providing lubricants and
10 functional fluids with improved frictional properties. Vibrations (shudder or stick
slip) in automatic transmissions (AT) caused by continuous slip torque converterclutches and shifting clutches are greatly reduced or elimin~ted by the use of the
fluids of this invention in said transmissions.
Automatic tr~ncmission fluids (ATF) are well known in the art. In general
15 however, automatic transmission suppliers and manufacturers specify
performance characteristics of the transmission operating with a fluid rather than
fluid composition for use in the transmission. It is then up to fluid providers to
formulate fluids which meet performance characteristics. Recently, performance
requirements for ATFs Service Fills have become more stringent with publication
20 of DEXTRON-III ATF Specification by General Motors, GM 6297M, April,
1993. The Specification is available from General Motors, Material Engineering
Transmissions, M/C 748 Ypsilanti, MI 48197 and is herein incorporated by
reference.
Low frequency vibration in continuous slip torque converter clutches
25 (CSTCC) has been defined as shudder. The shudder vibration is related to stick
slip friction characteristics of the engaged CSTCC rotating at slow speeds.
Further, shudder has two components, initial shudder and shudder durability. Thelatter is shudder which develops over time. Compositions of the present invention
were tested for anti-shudder properties when compared to commercial ATF
30 formulations both for initial shudder and shudder durability. It was found that
-
2 ~ 7~3-~
`
compositions of this invention eliminated or greatly reduced shudder and shudderdurability problems whereas no commercial ATF available performed as well.
Compositions of the instant invention and commercial ATF's were tested
in a Chrysler~ minivan with a 4 lTE tr~nsmission. The compositions of the instant
5 invention were by far superior to commercial ATF's in anti-shudder and anti-
shudder durability tests. Detailed descriptions of anti-shudder testing procedures
are given in SAE TECHNICAL PAPER SERIES NO. 941883, Friction and
Stick-Slip Durability Testing of ATF by Ward et al, presented at SAE
International Fuels and Lubricants Meeting and Exposition, Baltimore, Maryland,
Oct. 17-20, 1994. This publication is available from SAE International, 400
Commonwealth Drive, Warrendale, PA 15096-0001 U.S.A.
In general, automatic transmission fluids comprise a base oil and
additives. The base oil may be from natural sources; mineral and plant oils, andfrom synthetics and will be of the proper viscosity for their intended use.
15 Additives are then incorporated into the base oil with those incorporated being
dependent upon the properties that the fluid formulator is striving for. Additives
generally can be roughly broken into two groups, chemically inert and chemically active additives as listed below:
Chemically Active Additives Chemically Inactive Additives
anti-oxidants viscosity improvers
corrosion inhibitors friction modifiers
rust inhibitors defoamers
anti-wear agents pour point depressants
dispersants
detergents
seal swell agents
Formulations for ATF's and functional fluids cont~ining some or all of the
above additives in a select base oil are freely available in the patent literature. For
instance, U.S. Patent 4,209,587 to Koch lists lubricating/functional fluid
2 1 78D37
compositions with various combinations of base oils and additives. U.S. Patent
5,344,579 to Ohtani and Harley describes a friction modifier system for AT and
cites additive components for ATF's and their typical ranges. The disclosure of
both U.S. patents cited above are herein incorporated by reference. It must be
5 noted that the lines between chemically active and inactive additives are not so
distinct. Also, additives may well be multifunctional and are categorized above
only for the sake of convenience.
SUMMARY OF THE INVENTION
Despite the voluminous information and formulations available for ATF's,
none has been found which match the anti-shudder and shudder durability test
results demonstrated by the invention described herein.
This invention comprises a friction modifier additive package which when
incorporated into ATF' s provide an AT filled with said ATF with improved anti-
shudder and shudder durability performance. The additive package comprises:
A. an overbased alkali or alkaline earth metal salt component selected
from the group consisting of sulfonates, phenates, salicylates, carboxylates andmixtures thereof;
B. friction modifiers; said friction modifiers comprising an alkoxylated
fatty amine and two friction modifier selected from the group consisting of:
fatty phosphites
fatty epoxides
borated fatty epoxides
fatty amines
borated alkoxylated fatty amines
fatty acid amides
fatty acid metal salts
glycerol esters
borated glycerol esters
fatty imidazolines.
~ ~ 7 ~
A key feature of the additive package of the instant invention is the
selection of alkoxylated fatty amines as a component of the friction modifier and
the use of non-borated overbased metal salts. These features distinguish this
invention from U.S. Patent 4,792,410 which is herein incorporated by reference.
s
DETAILED DESCRIPTION OF THE INVENTION
The ATF's formulated with the additive package are particularly effective
against shudder when used in AT's with continuous slip torque converter
clutches.
The additive package composition comprises mixtures of several friction
modifiers, and an overbased alkali metal or alkaline earth metal salt selected from
the group consisting of sulfonates, phenols, salicylates, carboxylates and mixtures
thereof which when dissolved in an oil of lubricating viscosity provides an ATF
with greatly improved shudder and shudder durability properties.
The first component of the package composition is the overbased metal
salts of organic acids which hav~e been found useful in assisting the frictionalproperties of ATF 's. Borated and non-borated overbased materials are described
in U.S. Patents 5,403,501 and 4,792,410 which are herein incorporated by
reference for disclosure pertinent hereto.
Preferred overbased organic salts are the sulfonate salts having a
substantially oleophilic character and which are formed from organic materials.
Organic sulfonates are well known materials in the lubricant and detergent arts.The sulfonate compound should contain on average from about 10 to about 40
carbon atoms, preferably from about 12 to about 36 carbon atoms and preferably
from about 14 to about 32 carbon atoms on average. Similarly, the phenates,
oxylates and carboxylates have a substantially oleophilic character.
While the present invention allows for the carbon atoms to be either
aromatic or in paraffinic configuration, it is highly preferred that alkylated
aromatics be employed. While naphthalene based materials may be employed, the
aromatic of choice is the benzene moiety.
2 1 781~37
The most preferred composition is thus an overbased monosulfonated
alkylated benzene, and is preferably the monoalkylated benzene. Typically, alkylbenzene fractions are obtained from still bottom sources and are mono- or di-
alkylated. It is believed, in the present invention, that the mono-alkylated
aromatics are superior to the dialkylated aromatics in overall properties.
It is desired that a mixture of mono-alkylated aromatics (benzene) be
utilized to obtain the mono-alkylated salt (benzene sulfonate) in the present
invention. The mixtures wherein a substantial portion of the composition contains
polymers of propylene as the source of the alkyl groups assists in the solubility of
the salt. The use of mono-functional (e.g., mono-sulfonated) materials avoids
crosslinking of the molecules with less precipitation of the salt from the lubricant.
It is preferred that the salt be "overbased". By overbasing, it is meant that
a stoichiometric excess of the metal be present over that required to neutralizethe anion of the salt. The excess metal from overbasing has the effect of
neutralizing acids which may build up in the lubricant. A second advantage is that
the overbased salt increases the dynamic coefficient of friction. Typically, theexcess metal will be present over that which is required to neutralize the anion at
about 10:1 to 30:1, preferably 11:1 to 18:1 on an equivalent basis.
The amount of the overbased salt utilized in the additive package is
typically from about 5% to about 30%, preferably from about 5% to about 25%,
and most preferably from about 10% to about 25% by weight of the total
composition. The weight percents are on an oil free basis. The overbased salt isusually made up in about 50% oil with a TBN range of 10-600.
A. Overbased Metal Salt of an Organic Acid
Organic Acids - The organic acids useful in making the overbased
compositions of the present invention include carboxylic acid, sulfuric acid,
phosphorus-cont~ining acid, phenol or mixtures of two or more thereof.
Carboxylic Acids - The carboxylic acids useful in m~king the salts of the
invention may be aliphatic or aromatic, mono- or polycarboxylic acid or acid
producing compounds. These carboxylic acids include lower molecular weight
2 1 7~7
carboxylic acids (e.g., carboxylic acids having up to about 22 carbon atoms suchas acids having about 4 to about 22 carbon atoms or tetrapropenyl-substituted
succinic anhydride) as well as higher molecular weight carboxylic acids.
Throughout the specification and in the appended claims, any reference to
5 carboxylic acids is intended to include the acid-producing derivatives thereofsuch as anhydrides, lower alkyl esters-, acyl halides, lactones and mixtures
thereof unless otherwise specifically stated.
The carboxylic acids of this invention are preferably oil-soluble and the
number of carbon atoms present in the acid is important in contributing to the
10 desired solubility of the borated salts (B). Usually, in order to provide the desired
oil-solubility, the number of carbon atoms in the carboxylic acid should be at
least about 8, more preferably at least about 18, more preferably at least about30, more preferably at least about 50. Generally, these carboxylic acids do not
contain more than about 400 carbon atoms per molecule.
The lower molecular weight monocarboxylic acids contemplated for use in
this invention include saturated and unsaturated acids. Examples of such useful
acids include dodecanoic acid, decanoic acid, oleic acid, steric acid, linoleic acid,
tall oil acid, etc. Mixtures of two or more such agents can also be used. an
extensive discussion of these acids is found in Kirk-Othmer "Encyclopedia of
20 Chemical Technology" Third Edition, 1978, John Wiley & Sons New York, pp.
814-871; these pages being incorporated herein by reference.
Examples of lower molecular weight polycarboxylic acids include
dicarboxylic acids and derivatives such as sebacic acid, cetyl malonic acid,
tetrapropylene-substituted succinic anhydride, etc. Lower alkyl esters of these
25 acids can also be used.
The monocarboxylic acids include is aliphatic acids. Such acids often
contain a principal chain having from about 14 to about 20 saturated, aliphatic
carbon atoms and at least one but usually no more than about four pendant
acyclic lower alkyl groups. Specific examples of such isoaliphatic acids include
2 ~ ;7 8 1~
10-methyltetradecanoic acid, 3-ethyl-hexadecanoic acid, and 8-methyl
octadecanoic acid.
The isoaliphatic acids include mixtures of branch-chain acids prepared by
the isomerization of commercial fatty acids (oleic, linoleic or tall oil acids) of, for
5 example, about 16 to about 20 carbon atoms.
The higher molecular weight mono- and polycarboxylic acids suitable for
use in making the salts are well known in the art and have been described in
detail, for example, in the following U.S., British and C~n~ n patents. U.S.
Patents 3,024,237; 3,172,892; 3,219,666; 3,245,910; 3,271,310; 3,277,746;
10 3,278,550; 3,306,907; 3,312,619; 3,341,542; 3,367,943; 3,374,174; 3,381,022;
3,454,607; 3,470,098; 3,630,902; 3,755,169; 3,912,764; and 4,368,133. British
Patents 944,136; 1,085,903; 1,162,436; and 1,440,219. C-~n~di~n Patent
956,397. These patents are incorporated herein by reference for their disclosureof higher molecular weight mono- and polycarboxylic acids and methods for
15 making the same.
A group of useful aromatic carboxylic acids are those of the formula:
X* (XIII)
Il
(C X* H )b
/
R*a Ar
\(X*3 H)
wherein Formula XIII, R* is an aliphatic hydrocarbyl group of preferably about 420 to about 400 carbon atoms, a is a number in the range of zero to about 4, Ar is
an aromatic group, X*~, x*2 and X*3 are independently sulfur or oxygen, b is a
number in the range of from I to about 4, c is a number in the range of 1 to about
4, usually 1 to 2, with the proviso that the sum of a, b and c does not exceed the
number of valences of Ar. Preferably, R* and a are such that there is an average
2 1 78037
of at least about 8 aliphatic carbon atoms provided by the R* in each compound
represented by Formula IXXX.
The aromatic group Ar in Formula XIII may have the same structure as
any of the aromatic groups Ar discussed below under the heading "Phenols".
5 Examples of the aromatic groups that are useful herein include the polyvalent
aromatic groups derived from benzene, naphthalene, anthracene, etc., preferably
benzene. specific examples of Ar groups include phenylenes and naphthylene,
e.g., methylphenylenes, ethoxyphenylenes, isopropylphenylenes,
hyroxyphenylenes, dipropoxynaphthylenes, etc.
Examples of the R* groups in Formula XIII include butyl, isobutyl,
pentyl, octyl, nonyl, dodecyl, and substituents derived from polymerized olefinssuch as polyethylenes, polypropylenes, polyisobutylenes, ethylenepropylene
copolymers, oxidized ethylene-propylene copolymers, and the like.
Within this group of aromatic acids, a useful class of carboxylic acids are
15 those of the formula
~ (COOH)b
R*6a-~ (XIV)
(OH)c
wherein in Formula XIV, R+6 is an aliphatic hydrocarbyl group preferably
20 cont~inin~? from about 4 to about 400 carbon atoms, a is a number in the range of
from zero to about 4, preferably 1 to about 3; b is a number in the range of I to
about 4, preferably I to about 2, c is a number in the range of 1 to about 4,
preferably 1 to about 2, and more preferably 1; with the proviso that the sum ofa, b and c does not exceed 6. Preferably, R+6 and a are such that the acid
`~ 21 7~l337
molecules contain at least an average of about 12 aliphatic carbon atoms in the
aliphatic hydrocarbon substituents per acid molecule.
Also useful are the aliphatic hydrocarbon-substituted salicyclic acids
wherein each aliphatic hydrocarbon substituent contains an average of at least
about 8 carbon atoms per substituent and I to 3 substituents per molecule. Saltsprepared from such salicyclic acids wherein the aliphatic hydrocarbon
substituents are derived from polymerized olefins, particularly polymerized lower
l-mono-olefins such as polyethylene, polypropylene, polyisobutylene,
ethylene/propylene copolymers and the like and having average carbon contents
of about 30 to about 400 carbon atoms are particularly useful.
The aromatic carboxylic acids corresponding to Formulae XIII and XIV
above are well known or can be prepared according to procedures known in the
art. Carboxylic acids of the type illustrated by these formulae and processes for
preparing their neutral and basic metal salts are well known and disclosed, for
example, in U.S. Patents 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092;
3,410,798 and 3,595,791.
Sulfonic acids - The sulfonic acids useful in making salts (B) of the
invention include the sulfonic and thiosulfonic acids. Generally they are salts of
sulfonic acids.
The sulfonic acids include the mono- or polynuclear aromatic or
cycloaliphatic compounds. The oil soluble sulfonates can be represented for the
most part by the following formulae:
R#l,--T--(SO3)b (XV)
R~2_(SO3),
(XV)
In the above Formulae XV and XVI, T is a cyclic nucleus such as, for example,
benzene, naphthalene, anthracene, diphenylene oxide, diphenylene sulfide,
petroleum naphthenes, etc.; Rl is an aliphatic group such as alkyl, alkenyl,
21 780~7
-10-
alkoxy, alkoxyalkyl, etc.; a is at least 1, and R~l" +T contains a total of at least
about 15 carbon atoms. R'Q is an aliphatic hydrocarbyl group cont~ining at leastabout 15 carbon atoms. Examples of R#2 are alkyl, alkenyl, alkoxyalkyl,
carboalkoxyalkyl, etc. Specific examples of R#2 are groups derived from
5 petrolatum, saturated and unsaturated paraffin wax, and polyolefins, includingpolymerized C2 C3, C4, C5, C6, etc., olefins containing from about 15 to 7000 ormore carbon atoms. The groups T, R~l and R#2 in the above Formula XV, a and b
are at least 1, and likewise in Formula XVI, a is at least 1.
Specific examples of oil-soluble sulfonic acids are mahogany sulfonic
10 acids; bright stock sulfonic acids; sulfonic acids derived from lubricating oil
fractions having a Saybolt viscosity from about 100 seconds at 100F to about
200 seconds at 210F; petrolatum sulfonic acids; mono- and poly-wax substituted
sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol, diphenylether, naphthalene disulfide, etc.; other substituted sulfonic acids such as alkyl
15 benzene sulfonic acids (where the alkyl group has at least 8 carbons), cetylphenol
mono-sulfide sulfonic acids, dilauryl beta naphthyl sulfonic acids, and alkaryl
sulfonic acids such as dodecyl benzene "bottoms" sulfonic acids.
Dodecyl benzene "bottoms" sulfonic acids are the material leftover after
the removal of dodecyl benzene sulfonic acids that are used for household
20 detergents. These materials are generally alkylated with higher oligomers. The
bottoms may be straight-chain or branched-chain alkylates with a straight-chain
dialkylate preferred.
The production of sulfonates from detergent m~nuf~ctured by-products by
reaction with, e.g., S03, is well known to those skilled in the art. See, for
25 example, the article "Sulfonates" in Kirk-Othmer "Encyclopedia of Chernical
Technology", Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley
& Sons, N.Y. (1969).
Also included are aliphatic sulfonic acids such as paraffln wax sulfonic
acids, unsaturated paraffln wax sulfonic acids, hydroxy-substituted paraffln was30 sulfonic acids, hexapropylene sulfonic acids, tetra-amylene sulfonic acids,
2~ 7~7
polyisobutene sulfonic acids wherein the polyisobutene contains from 20 to 7000
or more carbon atoms, chloro-substituted paraffm wax sulfonic acids, etc.,
cycloalpiphatic sulfonic acids such as petroleum naphthlene sulfonic acids,
lauryl cyclohexyl sulfonic acids, mono- or poly-wax-substituted cyclohexyl
sulfonic acids, etc.
With respect to the sulfonic acids or salts thereof described herein and in
the appended claims, it is intended herein to employ the term "petroleum sulfonic
acids" or "petroleum sulfonates" to cover all sulfonic acids or the salts thereof
derived from petroleum products. A useful group of petroleum sulfonic acids are
the mahogany sulfonic acids (so called because of their reddish-brown color)
obtained as a by-product from the m~n~lf~cture of petroleum white oils by a
sulfuric acid process.
Generally neutral and basic salts of the above-described synthetic and
petroleum sulfonic acids are useful in the practice of this invention.
Phosphorus-Containing Acids - The phosphorus-cont~ining acid may be
any of the acids described below under Component D- 1 or Component D-3 .
In a preferred embodiment, the phosphorus-cont~inin~ acid is the reaction
product of an olefin polymer and phosphorus sulfide. The olefin polymers
generally have a molecular weight of at least 150 up to about 48,000, preferablyfrom about 500 to about 5000. The polymers include homopolymers and
interpolymers of monolefins having from 2 to about 12 carbon atoms. Examples
of useful monolefins include ethylene, propylene, butylene, hexylene, etc .
Useful phosphorus sulfide-cont~ining sources include phosphorus
pçnt~sulfide, phosphorus esquisulfide, phosphorus heptasulfide and the like.
The reaction of the olefin polymer and the phosphorus sulfide generally
may occur by simply mixing the two at a temperature above 80C, preferably
between 100C and 300C. Generally, the products have a phosphorus content
from about 0.05% to about 10%, preferably from about 0.1% to about 5%. The
relative proportions of the phosphorizing agent to the olefin polymer is generally
21 78~i
from 0.1 part to 50 parts of the phosphorizing agent per 100 parts of the olefinpolymer.
The phosphorus-containing acids useful in the present invention are
described in U.S. Patent 3,232,883 issued to Le Suer. This reference is herein
S incorporated by reference for its disclosure to the phosphorus-cont~ining acids
and methods for preparing the same.
Phenols - The phenols useful in making the borated salts of the invention
can be represented by the formula:
R ~--Ar ()b (XVIII)
wherein in Formula XVIII, R#3 is a hydrocarbyl group of from about 4 to about
400 carbon atoms; Ar is an aromatic group; a and b are independently numbers of
at least one, the sum of a and b being in the range of two up to the number of
displaceable hydrogens on the aromatic nucleus or nuclei of Ar. Preferably, a and
b are independently numbers in the range of 1 to about 4, more preferably 1 to
about 2. R#3 and a are preferably such that there is an average of at least about 8
aliphatic carbon atoms provided by the R#3 groups for each phenol compound
represented by Formula IVIII.
While the term "phenol" is used herein, it is to be understood that this
term is not intended to limit the aromatic group of the phenol to benzene.
Accordingly, it is to be understood that the aromatic group as represented by
"Ar" in Formula XII, as well as elsewhere in other formulae in this specification
and in the appended claims, can be mononuclear such as a phenyl, a pyridyl, or athienyl, or polynuclear. The polynuclear groups can be of the fused type whereinan aromatic nucleus is fused at two points to another nucleus such as found in
naphthyl, anthranyl, etc. The polynuclear group can also be of the linked type
wherein at least two nuclei (either mononuclear or polynuclear) are linked
through bridging linkages to each other. These bridging linkages can be chosen
21 78~37
`
from the group consisting of alkylene linkages, ether linkages, keto linkages,
sulfide linkages, polysulfide linkages of 2 to about 6 sulfur atoms, etc.
The number of aromatic nuclei, fused, linked or both, in Ar can play a role
in determining the integer values of a and b in formula XVIII. For example, whenAr contains a single aromatic nucleus, the sum of a and be is from 2 to 6. When
Ar contains two aromatic nuclei, the sum of a and b is from 2 to 10. With a tri-nuclear Ar moiety, the sum of a and b is from 2 to 51. The value for the sum of a
and b is limited by the fact that it cannot exceed the total number of displaceable
hydrogens on the aromatic nucleus or nuclei of Ar.
The R#3 group in Formula XVIII is a hydrocarbyl group that is directly
bonded to the aromatic group Ar. R#3 preferably contains about 6 to about 80
carbon atoms, preferably about 6 to about 30 carbon atoms, more preferably
about 8 to about 25 carbon atoms, and advantageously about 8 to about 15
carbon atoms. Examples of R#3 groups include butyl, isobutyl, pentyl, octyl,
nonyl, dodecyl, 5-chlorohexyl, 4-ethoxypentyl, 3 -cyclohexyloctyl, 2,3,5
trimethylheptyl, and substituents derived from polymerized olefins such as
polyethylenes, polypropylenes, polyisobutylenes, ethylene-propylene copolymers,
chlorinated olefin polymers, oxidized ethylene-propylene copolymers, propylene
tetramer and tri(isobutene).
The overbasing is generally done such that the metal ratio is from about
1.05:1 to about 50:1, preferably 2:1 to about 30:1 and most preferably from
about 4:1 to about 25:1. The metal ratio is that ratio of metallic ions on an
equivalent basis to the anionic portion of the overbased material. This degree of
overbasing is reported as the Total Base Number (TBN). The prefel,ed TBN of
the detergent is in the range of 25- 200 as determined by ASTM method 2896D.
However, TBN ranges of 10-600 may be used.
2. The Inert Liquid Medium. The inert liquid medium when utilized
to obtain the borated product facilitates mixing of the ingredients. That is, the
overbased material tend to be rather viscous especially when the alk~line earth
metal components are utilized. Thus, the inert liquid medium serves to disperse
2 1 78~7
-14-
the product and to facilitate mixing of the ingredients. The inert liquid medium is
typically a material which boils at a temperature much greater than that of water
and which is useful in the end product for which the invention is intended.
Typically, the inert liquid medium is a member selected from the group
5 consisting of aromatics, aliphatics, alkanols and mineral oil and mixture thereo
The aromatics utilized are typically benzene or toluene while the aliphatics arematerials having from about 6 to about 600 carbon atoms. The alkanols may be
mono- or di-alkanols and are preferably those materials which have limited watersolubility. Typically, alkanols containing 10 or less carbon atoms are useful
10 herein. Mineral oil, when used as the inert liquid medium is as typically defined
by the ASTM standards.
The inert liquid medium may be omitted where, for example, the product
is extruded. In such cases mechanical mixing replaces the need for a solvent.
3. The Carbon Dioxide Component. The carbon dioxide content of
15 product (d) is typically greater than about 5% by weight. It is desirable that the
carbon dioxide content of product (d) be between 5.5% and about 12% by
weight. The weights given herein are by weight of the total product including the
inert medium. The carbon dioxide content of the products is obtained by
acidifying the product to liberate all of the CO2 in the product. For purposes
20 herein, the terms carbon dioxide and carbonate are identical. That is, the
carbonate is the chemically incorporated form of the carbon dioxide and the latter
is the compound used to specify the amount of carbonate in the product. Thus,
the ratios expressed herein use the molecular weight (44) of carbon dioxide.
4. The boronatin~ a~ent. This is typically orthoboric acid. Also useful
25 herein are boron acid, boron anhydride, boron esters, and similar materials. The
boron content of the products of the present invention is typically greater than3%, preferably greater than 4% and most preferably greater than 5% by weight of
the product. It is also desirable that the weight percent of carbon dioxide in the
product (d) is at least 50% by weight of the boron in product (d). Preferably, the
21 78~3~
present carbon dioxide to the percent boron is greater than 75% and most
preferably greater than 100% by weight of the boron.
S. The water content of the product when it is finished is typically
less than 3% by weight. At levels much greater than 2% by weight substantial
5 amounts of the boron can be lost by forming boron compounds which are soluble
in the water and which are separated off. If the separation does not occur during
processing, then during storage, the boron content may be dimini~hed by having
un~cceptably high levels of water in the product. More preferably, the water
content of the product is less than 1% by weight and most preferably less than
10 0.75% by weight.
6. The Processin~. The products herein are conventionally obtained
up to the point where the boron incorporation occurs. That is, the boronation
aspect to obtain the alkali metal or alkaline earth metal overbased sulfonate isdov~v,.s~leam from the carbonation facility. If desired, carbonation may continue;
lS however, such is not necessary and hinders the boronation in addition to raising
the cost of the product.
The mixture of overbased acid as defined above is treated at a
temperature less than that at which substantial foaming occurs. Such temperatureis typically less than 110C, more preferably less than 99C, and most preferably
20 between about 66C and about 88C. It is also desirable that the temperature is
raised during the boronation but not raised so rapidly as to cause substantial
foaming. not only does the foaming cause a loss of head space in the reaction
vessel with a concomitant blocking of reaction ports but the product is not
believed to be the same if it is rapidly liberated of carbon dioxide. That is, there is
25 an exchange reaction occurring between the carbon dioxide portion of the
overbased material and the boronating agent wherein boron polymers are
incorporated into the overbased material. Thus, the boronation is allowed to
occur without substantial foaming until the point where substantially no more
boron is taken up by the overbased material.
21 7~37
`
-16-
At the point where the boron is substantially chemically incorporated
within the overbased material, the temperature is then raised to a point in excess
of the boiling point of water within the mixture. Such temperatures are typically
in excess of 100C as the water tends to separate rapidly from the reaction massS at that temperature. conveniently, the temperature for removing the water is
between about 120C and 180C. As the boronation is substantially complete and
the carbon dioxide content of the product is stable, substantial foaming is avoided
at the point where the water is taken from the product. thus, little carbon dioxide
will be liberated between steps.
The product is typically recovered as the high carbonate content borated
product by allowing the product to cool, followed by suitable paçlf~ging Of
course, the product is slightly hygroscopic due to the high inorganic content and,
thus, protective pae~ ing is recommended. The product may also be recovered
by transferring it for downstream processing such as mixing it with additional
15 materials such as an oil of lubricating viscosity or other desired components for a
lubricant or a grease. A significant advantage is practicing the present invention
is that the boronation is brought about without alternatively raising and lowering
the temperature, especially during segmental addition of the boronating agent.
It is desired that the mean particle diameter of the products obtained
20 herein is less than 9 microns, preferably less than 8 microns and most preferably
less than 5 microns. Preferably, the particle size distribution is such that
substantially all of the particles are less than 9 microns, more preferably less than
8 microns and most preferably less than 5 microns. Thus, the products obtained
herein are subst~nti~lly different than those known in the art in that the fine
25 particle size obtained herein allows effective dispersion in an oil or grease thereby
giving effective protection for the metal surfaces with which the product is
brought into contact. General guidance in dete"..ining the particle size herein is
found in the Textbook of Polymer Science by Billmeyer, fourth printing, March,
1966, Library of Congress Catalog No. 62.18350.
- 2 1 ;~ ~37
B. Friction Modifiers. The second component of the package is the
friction modifier. The friction modifier comprises an alkoxylated fatty amine and
at least two other friction modifiers selected from the group con.~i~ting fatty
phosphites, fatty epoxides, borated fatty epoxides, fatty amines, borated
alkoxylated fatty amines, fatty acid amides, glycerol esters, borated glycerol
esters, fatty imidazolines or mixtures thereof.
1. The phosphites are generally of the formula (RO)2PHO. The
preferred dialkylated phosphite as shown in the prece-lin.~ formula is typicallypresent with a minor amount of monoalkylated phosphite of the formula
(RO)(HO)PHO.
In the above structure of the phosphite, the term "R" has been referred to
as an alkyl group. It is, of course, possible that the alkyl is alkenyl and thus the
terms "alkyl" and "alkylated", as used herein, embrace other than saturated alkyl
groups within the phosphite. The phosphite utilized herein is one having
sufficient hydrocarbyl groups to render the phosphite substantially oleophilic and
further that the hydrocarbyl groups are preferably subst~nti~lly unbranched.
Many suitable phosphites are available commercially and may be
synthesized according to U.S. Patent 4,752,416 to Scharf et al which is
incorporated herein by reference.
It is preferred that the phosphite contain from about 8 to about 24 carbon
atoms in each of the fatty radicals described as "R". Preferably, the fatty
phosphite contains from about 12 to about 22 carbon atoms in each of the fatty
radicals, most preferably from about 16 to about 20 carbon atoms in each of the
fatty radicals. It is highly preferred that the fatty phosphite be formed from oleyl
groups, thus having 18 carbon atoms in each fatty radical.
2. Other friction modifiers which are useful herein are borated fatty
epoxides, borated glycerol monocarboxylates, and borated alkoxylated fatty
amines. Borated fatty epoxides are known from Can~di~n Patent No. 1,188,704
which patent is incorporated herein by reference. The oil-soluble boron
21 78037
-18-
containing compositions of Davis are prepared by reacting at a temperature from
about 80C to about 250C,
(A) at least one of boric acid or boron trioxide with
(B) at least one epoxide having the formula
s
RlR2C[o]CR3R4
wherein each of Rl, R2, R3 and R4 is hydrogen or an aliphatic radical, or any two
thereof together with the epoxy carbon atom or atoms to which they are
10 attached, form a cyclic radical, said epoxide cont~ining at least 8 carbon atoms.
As will be apparent, the borated fatty epoxides are characterized by the
method for their preparation which involves the reaction of two materials.
Reagent A may be boron trioxide or any of the various forms of boric acid
including metaboric acid (HBO2), orthoboric acid (H3BO3) and tetraboric acid
15 (H2B407). Boric acid, and especially orthoboric acid, is prefe"ed.
Reagent B is at least one epoxide having the above formula and
cont~ining at least 8 carbon atoms. In the formula, each of the r values is mostoften hydrogen or an aliphatic radical with at least one being an aliphatic radical
cont~ining at least 6 carbon atoms. The term "aliphatic radical" includes aliphatic
20 hydrocarbon radicals (e.g., hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl,stearyl, hexenyl, oleyl), preferably free from acetylenic unsaturation; substit~lted
aliphatic hydrocarbon radicals including substituents such as hydroxy, nitro,
carbalkoxy, alkoxy and alkylthio (especially those cont~inin~ a lower alkyl
radical; i.e., one cont~ining 7 carbon atoms or less); and hetero atom-cont~ining
25 radicals in which the hetero atoms may be, for example, oxygen, nitrogen or
sulfur. The aliphatic radicals are preferably alkyl radicals, and more preferably
those cont~ining from about 10 to about 20 carbon atoms. Mixtures of epoxides
may be use; for example, commercial available C,4-,6 or C,4-,8 epoxides and the
like, wherein Rl is a mixture of alkyl radicals having two less carbon atoms than
2 1 7~1~37
-19-
the epoxide. Most desirably, Rl is a straight-chain alkyl radical and especially the
tetradecyl radical.
Further useful epoxides are those in which any two of the R radicals form
a cyclic radical, which may be alicyclic or heterocyclic. Examples are n
5 butylcyclopentene oxide, n-hexylcyclohexene oxide, methylenecyclo-octene oxide and 2-methylene-3-n-hexyltetrahydrofuran oxide.
The borated fatty epoxides may be prepared by merely blending the two
reagents and heating them at temperature from about 80 to about 250C,
preferably from about 100 to about 200C, for a period of time sufficient for
10 reaction to take place. If desired, the reaction may be effected in the presence of
a substantially inert, normally liquid organic diluent such as toluene, xylene,
chlorobenzene, dimethylformamide or the like, but the use of such diluents is
usually unnecessaly. During the reaction, water is evolved and may be removed
by di.ctill~tion.
The molar ratio of reagent A to reagent B is generally between about
1:0.25 and about 1:4. Ratios between 1:1 and about 1:3 are prerelled, with 1:2
being an especially preferred ratio.
It is frequently advantageous to employ a catalytic amount of an alkaline
reagent to facilitate the reaction. Suitable alkaline reagents include inorganic20 bases and basic salts such as sodium hydroxide, potassium hydroxide and sodium
carbonate; metal alkoxides such as sodium methoxide, potassium t-butoxide and
calciumethoxide; heterocyclic amines such as piperidine, morpholine and
pyridine; and aliphatic amines such as n-butylamine, di-n hexylamine and tri-n-
butylamine. The preferred alkaline reagents are the aliphatic and heterocyclic
25 amines and especially tertiary amines. When the prefel~ed method involving the
"heel" is used, the alkaline reagent is typically added to the blend of the "heel"
with reagent A.
The molecular structures of the compositions of this invention are not
known with certainty. During their preparation, water is evolved in near
30 stoichiometric amounts for conversion of boric acid to boron trioxide when
21 78D37
-20-
reagent A is boric acid, and gel permeation chromatography of the composition
prepared from boric acid and a C16 alpha-olefin oxide mixture in a 1 :2 molar ratio
indicates the presence in substantial amounts of three constituents having
approximate molecular weights of 400, 600 and 1200.
3. The borated amines are generally known from European published
application Nos. 84 302 342.5 filed Apr. 5, 1984 and 84 307 355.2 filed Oct. 25,1984, both authorized by Reed Walsh, and U.S. Patent 4,622,158 by the same
inventor.
The borated amine friction modifiers are conveniently plepared by the
reaction of a boron compounds selected from the group consieting of boric acid,
boron trioxide and boric acid esters of the formula B(OR)3 wherein R is a
hydrocarbon-based radical containing from 1 to about 8 carbon atoms and
preferably from about 1 to about 4 carbon atoms with an amine selected from the
group consisting of hydroxy containing tertiary amines corresponding to the
formulae
B--(ORI )xNR2R3 (A)
and
B--[(ORI)xZ]3 (B)
wherein Z is an imidazolene radical, Rl is each formula is a lower alkylene based
radical containing from 1 to about 8 carbon atoms, R2 is a radical selected fromthe group consisting of hydrocarbon based radicals cont~ining from 1 to about
100 carbon atoms and alkoxy radicals of the structure H(oR4)y--where R4 is a
lower alkylene based radical containing from 1 to about 8 carbon atoms, R3 and
R5 (pendent from the ethylenic carbon in the 2 position in the imidazolene (Z)
radical) are each hydrocarbon based radicals con~ining from 1 to about 100
carbon atoms, x and y are each an integer ranging from at least 1 to about 50 and
the sum of x+y is at most 75.
` 21 7~37
In one embodiment, the amines useful in preparing the organo-borate
additive compositions are those tertiary amines corresponding to (A) above
wherein R2 is an alkoxy radical of the structure H(oR4)y--wherein R4 is a lower
alkylene radical cont~ining from 1 to about 8 carbon atoms and R3 is an aliphatic
5 based hydrocarbon radical containing from about 8 to about 25 carbon atoms,
and preferably from about 10 to about 20 carbon atoms and x and y are each an
integer ranging from at least 1 to about 25 and wherein the sum of x+y is at most
50, and those tertiary amines cont~ining the imidazoline structure above whereinRl is a lower alkylene radical containing from 1 to about 8 carbon atoms, R5 is an
10 aliphatic based hydrocarbon radical, preferably alkyl or alkenyl based radical,
containing from about 8 to about 25 carbon atoms and preferably &om about 10
to about 20 carbon atoms.
rlerel,ed tertiary amines useful in preparing the multi-functional organo-
- borate additive compositions are those tertiary amines corresponding to formula
lS (A) above wherein R2 is an alkoxy radical of the structure H(oR4)y--, wherein R1
and R4 are individually ethylene or propylene radicals, R3 is an alkyl or an alkenyl
based hydrocarbon radical cont~ining from about 10 to about 20 carbon atoms, x
and y are each an integer ranging from at least I to about 9 and preferably from at
least 1 to about 5 and the sum of x+y is at most 10 and preferably at most S, i.e.,
20 the sum of x+y ranges from about 2 to about 0 and preferably from about 2 to
about 5 respectively. Amines, per se, such as oleyl amines are userul as
friction modifiers herein.
As used in this specification, the term "hydrocarbon-based radical"
denotes a radical having a carbon atom directly attached to the remainder of the25 molecule and having predominantly hydrocarbon character within the context of this invention. Such radicals include the following:
(1) Hydrocarbon radicals; that is, aliphatic, (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-
substituted aromatic, aromatic-substituted aliphatic and alicyclic radicals, and the
30 like aswell as cyclic radicals wherein the ring is completed through another
~178~
portion of the molecule (that is, any two indicated hydrocarbon radicals, e.g., R2
and R3, may together form an alicyclic radical and such radical may contain
hetero atoms such as nitrogen, oxygen and sulfur). Such radicals are known to
those skilled in the art; representative examples are examples of such radicals as
5 represented by R2, R3 and R5 in the formulae above include methyl, ethyl, butyl,
hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, eicosyl, cyclohexyl, phenyl and
naphthyl and the like including all isomeric forms of such radicals and when R2
and R3 together form an alicyclic radical, then examples of such radicals include
morpholinyl, piperidyl, piperazinyl, phenothiazinyl, pyrrolyl, pyrrolidyl,
10 thiazolidinyl and the like.
(2) Substituted hydrocarbon radicals; that is, radicals cont~inin~ non
hydrocarbon substituents which, in the context of this invention, do no alter the
predomin~ntly hydrocarbon character of the radical. Those skilled in the art will
be aware of suitable substituents; representative examples are hydroxy (H0--);
alkoxy (R0--); carbalkoxy (R02C--); acyl [RC(0--]; acyloxy (RC02--);
carboxamide (H2NC(0)--); acylimidayl; [RC(NR)--]; and alkylthio (RS--) and
halogen atoms (e.g.,F,Cl,Br and I).
Hetero radicals; that is, radicals which, while predomin~ntly hydrocarbon,
contain atoms other than carbon present in a chain or ring otherwise composed ofcarbon atoms. Suitable hetero atoms will be apparent to those skilled in the artand include, for example, nitrogen, oxygen and sulfur.
In general, no more than about three substituents or hetero atoms, and
preferably no more than one, will be present for each 10 carbon atoms in the
hydrocarbon-based radical.
Terms such as "alkyl-based radical," "alkenyl-based radical" and alkylene-
based radical" and the like have analogous me~nin~.~ with respect to alkyl and
aryl radicals and the like.
Representative examples of the tertiary amine compounds useful in
preparing the organo-borate compounds of this invention include
monoalkoxylated amines such as dimethylethanolamine, diethylethanolamine,
2 ~ 7~037
`
-23 -
dibutylethanolamine, diisopropylethanolamine, di(2-ethylhexyl)ethanolamine,
phenylethylethanolamine, and the like and polyalkoxylated amines such as
methyldiethanolamine, ethyl diethanolamine, phenyldiethanolamine,
diethyleneglycol mono-N-morpholinoethyl ether, N-(2-hydroxyethyl)thiazoli-
5 dine, 3-morpholinopropyl-(2 hydroxyethyl)cocoamine, N-(2-hydroxy-ethyl)-N-
tallow-3-aminomethylpropionate, N (2-hydroxyethyl)-N-tallow acet~mide, 2-
oleoylethyl(2-hydroxyethyl)tallowamine, N [N'-dodecenyl]; N'-[2-hydroxy-
ethylaminoethyl]thiazole, 2-methoxyethyl-(2 hydroxyethyl)tallowamine, l-[N-
dodecenyl; N-2-hydroxyethyl-aminoethyl]imidazole, N-N'-octadecenyl-N'-2-
10 hydroxyethyl-aminoethyl] phenothiazine, 2 hydroxydicocamine, 2-hept~decçnyl- 1
-(2-hydroxyethylimidazoline, 2-dodecyl- 1 -(5 hydroxypentyl-imidazoline, 2-(3-
cyclohexyl propyl)-1-(2-hydroxyethyl-imidazoline) and the like.
An especially preferred class of tertiary amines useful in preparing the
organo borate compounds of the invention is that constihltin~ the commercial
15 alkoxylated fatty amines known by the trademark "ETHOMEEN" and available
from the Armak Company. Representative examples of these ETHOMEEN is
ETHOMEEN C/12(bis[2 hydroxyethyl]cocoamine); ETHOMEEN C/20
(polyoxyethylene[10]cocoamine); ETHOMEEN S/12(bis[2-
hydroxyethyll]soyamine); ETHOMEEN T/12(bis[2 hydlo~yetll~l]tallowamine);
20 ETHOMEEN T/l5(polyoxyethylene-[5]tallowamine); ETHOMEEN 0/12(bis[2-
hydroxyethyl] oleyl-amine; ETHOMEEN 18/ 12(bis[2
hydroxyethyl]octadecylamine; ETHOMEEN 18/25
polyoxyethylene[l5]octadecylamine and the like. Of the various ETHOMEEN
compounds useful in repairing the organo borate additive compounds of the
25 invention, ETHOMEEN T/12 is most preferred. Fatty amines, as well as being
commercially available are also described in U.S. Patent 4,741,848 which is
hereby incorporated by reference herein.
If desired, the tertiary amine reactants represented by formulae (A) and
(B) above may be reacted first with elemental sulfur to sulfurize any carbon-to-
30 carbon double bond unsaturation which may be present in the hydrocarbon based
21 78a37
-24-
radicals R2, R3 and Rs when these radicals are, for example, alkenyl radicals (e.g.,
fatty oil or fatty acid radicals)., Generally the sulfurization reaction will becarried out at temperatures ranging from about 100C to about 250C, and
preferably from about 150C to about 200C. The molar ratio of sulfur to amine
can range from about 0.5:1.0 to about 3:0:1.0 and preferably 1:0:1Ø Although,
generally no catalyst is required to promote sulfurization of any carbon-to-carbon
double bond unsaturation which may be present in any tertiary amine reactant
useful in preparing the organo-borate compositions of this invention, catalysts
may be employed, if desired. If such catalysts are employed, preferably, such
catalysts are tertiary hydrocarbon substituted amines, most preferably,
trialkylamnes. Representative examples of which include tributylamine,
dimethyloctylamine, triethylamine and the like.
The organo-borate additive friction modifiers can be prepared by adding
the boron reactant, preferably boric acid, to at least one of the above defined
tertiary amine reactants, in a suitable reaction vessel, and heating the res~lltin~
reaction mixture at a temperature ranging from about 50 to about 300C with
continuous stirring. The reaction is continued until by-product water ceases to
evolve from the reaction mixture indicating completion of the reaction. The
removal of by-product water is facilitated by either blowing an inert gas, such as
nitrogen, over the surface of the reaction mixture or by conducting the reactionat reduced pressures. Preferably the reaction between the boron reactant and thetertiary amine will be carried out at temperatures ranging from about 100C to
about 250C and most preferably between about 150C and 230C while blowing
with nitrogen.
Although normally the amines will be liquid at room temperature, in those
instances where the amine reactant is a solid or semi-solid, it will be necessqry to
heat the amine to above its melting point in order to liquify it prior to the
addition of the boron-containing reactant thereto. Those of ordinary skill in the
art can readily determine the melting point of the amine either from the generalliterature or through a simple melting point analysis.
2 1 78~37
Generally, the amine reactant alone will serve as the solvent for the
reaction mixture of the boron containing reactant and amine reactant. However,
if desired, an inert normally liquid organic solvent can be used such as mineraloil, naphtha, benzene, toluene or xylene can be used as the reaction media. Where
5 the organo-borate additive compound is to be added directly to a lubricating oil,
it is generally preferred to conduct the reaction merely using the amine reactant
as the sole solvent.
The alkoxylated fatty amines, and fatty amines themselves are generally
useful as components of this invention. Both types of amines are commercially
10 available.
The borated fatty acid esters of glycerol are prepared by borating a fatty
acid ester of glycerol with boric acid with removal of the water of reaction.
Preferably, there is sufficient boron present such that each boron will react with
from 1.5 to 2.5 hydroxyl groups present in the reaction ~ lure.
The reaction may be carried out at a temperature in the range of 60C to
135C, in the absence or presence of any suitable organic solvent such as
methanol, benzene, xylenes, toluene, neutral oil and the like.
4. Fatty acid esters of glycerol can be prepared by a variety of
methods well known in the art. Many of these esters, such as glycerol
20 monooleate and glycerol tallowate, are manufactured on a commercial scale. The
esters useful are oil-soluble and are preferably prepared from C8 to C22 fatty acid
or mixtures thereof such as are found in natural products. The fatty acid may besaturated or unsaturated. Certain compounds found in acids from natural sources
may include licanic acid which contains one keto group. Most ~)refelled C8 to C22
25 fatty acids are those of the formula RCOOH wherein R is alkyl or alkenyl.
The fatty acid monoester of glycerol is preferred, however, mixtures of
mono and diesters may be used. Preferably any mixture of mono- and diester
contains at least 40% of the monoester. Most preferably, mixtures of mono- and
diesters of glycerol contain from 40 to 60 percent by weight of the monoester.
2178~37
-26-
For example, commercial glycerol monooleat contains a mixture of from 45% to
55% by weight monoester and from 55% to 45% diester.
Preferred fatty acids are oleic, stearic, isostearic, palmitic, myristic,
palmitoleic, linoleic, lauric, linolenic, and eleostearic, and the acids from the
5 natural products tallow, palm oil, olive oil, peanut oil, corn oil, Neat's foot oil
and the like. A particularly preferred acid is oleic acid. The borated fatty acid
esters are conveniently stabilized against hydrolysis by reacting the esters with an
alkyl or alkenyl mono-or bis succinimide.
Additional ingredients which may be included in lubricant and functional
10 fluid of the present invention are fatty acid amides which are useful as additional
friction modifiers, particularly for reducing the static coefficient of friction.
In general a fatty acid with ammonia is an organic amine to produce the
desired amide. Also, many amides are commercially available. Also commercially
available are the fatty imidazolines which comprise a part of this invention.
A sulfurized olefin is included in the present invention as a friction
modifier which also functions as an extreme pressure agent. Extreme presswe
agents are materials which retain their character and prevent metal to metal
damage, e.g., contact, when gears are engaged and meshed. The sulfurization of
olefins is generally known as is evidenced by U.S. Patent No. 4,191,659 as
previously disclosed.
The sulfurized olefins which are useful in the present invention are those
materials formed from olefins which have been reacted with sulfur. Thus, an
olefin is defined as a compound having a double bond connecting two aliphatic
carbon atoms. In its broadest sense, the olefin may be defined by the formula
RlR2C=CR3R4, wherein each of Rl, R2, R3 and R4 is hydrogen or an organic
radical. In general, the R values in the above formula which are not hydrogen
may be satisfied by such groups as --C(R5)3,--CooR5,--CoN(R5)2,--
CooN(R5)4,--COOM,--CN,--C(R5)=C(R5)2,--C(R5)2=Y--X,--YR5 or--Ar.
Each R5 is independently hydrogen, alkyl, alkenyl, aryl, substituted alkyl,
substituted alkenyl or substituted aryl, with the proviso that any two R5 groups
2 1 78Q37
-27-
can be alkylene or substituted alkylene whereby a ring of up to about 12 carbon
atoms is formed;
M is one equivalent of a metal cation (preferably Group I or II, e.g.,
sodium, potassium, magnesium, barium, calcium);
X is halogen (e.g, chloro, bromo, or iodo);
Y is oxygen or divalent sulfur; and
Ar is an aryl or substituted aryl radical of up to about 12 carbon atoms.
Any two of R', R2, R3 and 1~4 may also together form an alkylene or
substituted alkylene group; i.e., the olefinic compound may be alicyclic.
The nature of the substituents in the substituted moieties described above
are not normally a critical aspect of the invention and any such substituent is
useful so long as it is, or can be made compatible, with lubricating environments
and does not interfere under the contemplated reaction conditions. Thus,
substituted compounds which are so unstable as to deleteriously decompose
15 under the reaction conditions employed are not contemplated. However, certainsubstituents such as keto or aldehydo can desirably undergo sulfurization. The
selection of suitable substituents is within the skill of the art of may be
established through routine testing. Typical of such substituents include any ofthe above-listed moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl,
20 sulfonate, nitro, phosphate, phosphite, alkali metal mercapto and the like.
The olefinic compound is usually one in which each R value which is not
hydrogen is independently alkyl, alkenyl or aryl, or (less often) a corresponding
~ub.,~ led radical. Monoolefinic and diolefinc compounds, particularly the
former, are prefe"ed, and especially terminal monoolefinic hydrocarbons; that is,
25 those compounds in which R3 and R4 are hydrogen and R' and R2 are alkyl or
aryl, especially alkyl (that is, the olefin is aliphatic). Olefinic compounds having
about 3 to 30 and especially about 3 to 18 (most often less than 9) carbon atomsare particularly desirable.
Isobutene, propylene and their oligomers such as dimers, trimers and
30 tetramers, and mixtures thereof are especially preferred olefinic compounds. Of
2 1 7~ 7
'_
these compounds, isobutylene and diisobutylene are particularly desirable because
of their availability and the particularly desirable because of their availability and
the particularly high sulfur containing composition which can be prepared
therefrom.
S Also included in the additive package are extreme pressure
agents/antiwear compositions which protect moving parts from wear. These
components act by coating metal parts with a protective film. Preferred antiwearagents are metal salts of phosphorodithioic acid. The metals are Group II metalssuch as aluminum. tin. cobalt, lead, molybdenum, m~ng~nese, nickel and zinc
with zinc being preferred. Mixtures of two or more metal salts may be used.
The phosphorodithioic acid are represented by formula
R10~
/PSSH
R20
wherein Rl and R2 are the same or different and Rl and R2 are hydrocarbon based
groups.
The phosphorus acids can be prepared by methods well known in the art
and generally are prepared by the reaction of phosphorus pent~slllfide (P2S5) with
an alcohol or a phenol, or a mixture of alcohols. The reaction involves mixing at
a te.llpe,~ re of about 20 to about 200C, four moles of the alcohol or phenol
with one mole of phosphorus pentasulfide. Hydrogen sulfide is
liberated in this reaction.
Preferably, the hydrocarbon-based groups in the compounds useful as
component (I) according to this invention are free from acetylenic and usually
also from ethylenic unsaturation and have from I to about 50 carbon atoms,
preferably 1 to about 30 carbon atoms, and more preferably from about 3 to
about 18 carbon atoms. R' and R2 are most often identical, although they may be
different and either or both may be mixtures. The groups are usually
hydrocarbon, preferably alkyl, and most desirably branched alkyl. Examples of R'
3 7
-29-
and R2 groups include isopropyl, isobutyl, 4-methyl-2-pentyl, 2-ethylhexyl,
isooctyl, etc.
The metal salts of the phosphorodithioic acid are prepared by reacting the
acid with suitable metal bases. The metal bases include the free metals
5 enumerated above and their oxides, hydroxides, alkoxides and basic salts.
Examples are sodium hydroxide, sodium methoxide, sodium carbonate,
potassium hydroxide, potassium carbonate, magnesium oxide, magnesium
hydroxide, calcium acetate, zinc oxide, zinc acetate, lead oxide, nickel oxide and
the like.
The temperature at which the metal salts of this invention are prepared is
generally between about 30 and about 150C, preferably up to about 125C.
It is frequently advantageous to conduct the reaction in the presence of a
substantially inert, normally liquid organic diluent such as naphtha, benzene,
xylene, mineral oil or the like. If the diluent is mineral oil or is physically and
chemically similar to mineral oil, it frequently need not be removed before using
the metal salts in the composition, concentrates and functional fluids of the
nvention.
The preparation of the metal salts useful in this invention is illustrated by
the following examples. All parts and percentages are by weight.
The term "neutral salt" refers to salts characterized by metal content equal
to that which would be present according to the stoichiometry of the metal and
the particular organic compound reacted with the metal. Thus, if a
phosphorodithioic acid, (RO)2PSSH, is neutralized with a basic metal compound,
e.g., zinc oxide, the neutral metal salt produced would contain one equivalent of
zinc for each equivalent of acid, i.e., [(RO)2PSS]2Zn.
However, with the present invention, the metal product can contain more
or less than the stoichiometric amount of metal. The products cont~inin~ less
than the stoichiometric amount of metal are acidic materials. The products
containing more than the stoichiometric amount of metal are overbased materials.For example, salts containing ~0% of the metal present in the corresponding
2 1 78Q37
-30-
neutral salt are acidic, while salts containing 110% of the metal present in thecorresponding neutral salt are overbased. The metal components may have about
80% to about 200%, preferably about 100% to about 150%, more preferably
about 100% to about 135%, and advantageously about 103% to about 110% of
5 the metal present in the corresponding neutral salt.
Preferred metal salt of the present invention is zinc diisooctyl
dithiophosphate and zinc dibenzyl dithiophosphate.
The dithiophosphates are present in the additive package at about 5-20
weight percent and in the fluid blend at 0.1-5% by weight. The prerelled range is
10 .1-3% of the fluid blend.
It should be noted that the zinc dithiophosphate also serves an antioxidant
function.
For a discussion of phosphorus cont~ining metal salts see Grover in U.S.
Patent 4,466,894 which is incorporated by reference for disclosure pertinent to
15 this invention.
The sulfurization of such compounds is conducted as is known in the art
and thus no further discussion of the sulfurized olefin component is given at this
point.
The amount of the friction modifier employed in the additive package of
20 the present invention is typically from about 0.1% to about 20%, preferably from
about 1.0% to about 12%, and most preferably from about 0.5% to about 10 by
weight of the total composition. Said percentages are on an oil free basis.
Several additional components are desirably added to the ATF fluid of the
present invention for instance Viscosity Index Modifiers (VIM~ may be added in
25 the weight range of up to 30% of the final ATF blend based on an oil free basis
for the VIM. As is well known in the art, useful viscosity index improvers are
polyisobutylenes, polymerized and co-polymerized alkyl meth~crylates, and
mixed esters of styrene maleic anhydride interpolymers reacted with nitrogen
containing compounds. The molecular weight of the VIM is selected by the
30 formulation to give the final ATF the desired viscosity.
2 1 78037
As is well known in the art, some of the listed-above VIM are classified as
dispersant-viscosity modifiers (dispersant-VM) because of their dual function. Adetailed description of dispersant-VM is presented in U.S. patent 4,594,378
which is incorporated herein by reference for its disclosure of dispersant-VM.
S The dispersant-VM disclosed in the '378 patent are (B-l), at least one nitrogen-
cont~ining ester of a carboxylic-cont~inin~ interpolymer and/or (B-2), at least
one oil-soluble acrylate-polymerization product of at least one acrylate ester, or a
mixture of (B-1) and (B-2)
Commercially available dispersant-VM are sold under trade names
Acryloid~ 1263 and 1265 by Rohm and Haas~, Viscoplex~ SlS1 and 5089 by
Rohm-GMBH0 and Lubrizol~ 3702 and 3715. Dispersant-VM may be used in
the final ATF blend at the same level as the viscosity index improvers describedabove. A prefe~led range for the dispersant-viscosity modifier in the final ATF is
in the range of 0.5-10 weight percent based on the weight of the ATF.
lS Other components which the final additive package may contain
properties are dibutylphosphite antiwear agent in a weight percent range of 0.1-S
based on the final ATF weight; synthetic seal swell agent comprising a sulfolaneor equivalent in the amount of 0. I-S weight based on the weight of the final ATF
weight.
The lubricating compositions can also include at least one phosphorus
acid, ester or derivative thereof. The phosphorus acids, esters or derivatives
thereof include compounds selected from the group con~isting of phosphorus
acid esters or salts thereof, phosphites, phosphorus cont~ining amides,
phosphorus-cont~ining carboxylic acids or esters, phosphorus cont~ininp ethers
and mixtures thereof.
In one embodiment, the phosphorus acid, ester or derivative can be a
phosphorus acid, phosphorus acid ester, phosphorus acid salt, or derivative
thereof.- The phosphorus acids include the phosphoric, phosphonic, phosphinic,
and thiophosphoric acids including dithiophosphoric acid as well as the
monothiophosphoric, thiophosphinic and thiophosphonic acids.
21 7~Q37
-
-32-
Eighty-five percent phosphoric acid is the preferred compound for
addition to the fully-form~ ted ATF package and is included at a level of about
0.01-3 weight percent based on the weight of the ATF.
Friction modifiers also include metal salts of fatty acids. Preferred cations
are zinc, magnesium, calcium, barium and sodium and any ~Ik~line, or alkaline
earth metals may be used. The salts may be overbased by including an excess of
cations per equivalent of amine. The excess cations is then treated with carbon
dioxide to form the carbonate. The metal salts are prepared by reacting a suitable
salt with the acid to form the salt, and where appropriate adding carbon dioxideto the reaction mixture to form the carbonate of any cation beyond that needed to
form the salt. A prerelled friction modifier is zinc oleate.
EXAMPLE
To a mixture of a fa~ty acid, oil and an aliphatic alcohol
(preferably about C~C8) at abouf 100-140C is added calcium
chloride in an amount in which Ca ion e~eeA~ the equivalents of
acid. The reaction is heated fo 200 for about two hours, then fhe
temperature is raised to 300C to distill solvent. The reaction is
cooled to 100-125 and carbonated with carbon dioxide to form
the overbased carbonate. The product is then taken up in oil and
provides a product roughly half and hay oil metal salt. The TBN
of a typical salt is 50-200.
Optionally antioxidants in the forms of s~llfides and mono- and di-
alkylated diphenylamines may be added to the final ATF blend in the amount of
up to 10 weight percent on an oil free basis each based on the weight of the final
ATF blend. Silicone anti-foam compositions may also be added to the final ATF
blend in the amount of about 40-400 parts per million based on ATF blend. Also
pour point depressants can be included in the final ATF blend at up to about
10% by weight based on the final weight of said ATF blend. An example of a
pour point depressant is an alkylene coupled napthalene.
2 1 78037
Also included in the final ATF blend is a dispersant or mixtures thereof in
weight percents of up to about 20% of the final blend on an oil free basis.
Dispersants in general comprise an oil soluble function such as a polybutene, a
polar group such as a polyamine or polyalcohol or mixture thereof, and a bridge
5 portion to join in the previous two. The bridge is commonly a succan molecule or
the like. The polybutene is preferably polyisobutylene with number average
molecular weight, Mn of 1000-2000, but Mn of 500-4000 may be useful.
Dispersants used in this invention comprise: (A) an acylated amine having
a base number in the range of about 45 to about 90, said acylated amine being the
10 product made by contacting (A)(I) at least one carboxylic acid acylating agent
with (A)(II) at least one polyamine, said polyamine (A)(II) being selected from
the group consisting of (A)(II)(a) a product made by contacting at least one
hydroxy material with at least one amine, (A)(II)(b) an alkylene polyamine
bottoms product, and (A)(II)(c) a product made by cont~A~cting a hydroxy material
15 with an alkylene polyamine bottoms product; (B) a boron compound; and (C) an
organic phosphorus acid or ester, or derivative of said phosphorus acid or ester.
In one embodiment, this composition further comprises (D) a thiocarbamate. In
one embodiment, this composition further comprises (E) a nitrogen cor~ ning
ester of a carboxy-contAining interpolymer. These compositions are useful as
20 additives for lubricants and functional fluids, and are particularly useful as
additives for automatic tr~n~mission fluids for enhancing the torque
characteristics such automatic trAn~mission fluids.
As used in this specification and in the appended claims, the term
"hydrocarbyl'l denotes a group having a carbon atom directly attached to the
25 remainder of the molecule and having a hydrocarbon or predo~ Al~liy
hydrocarbon character within the context of this invention. Such groups include
the following:
(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or alkenyl), alicyclic
(e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclic-substit~lted
30 aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well
21 78037
-34-
as cyclic groups wherein the ring is completed through another portion of the
molecule (that is, any two indicated substituents may together form an alicyclicgroup). Such groups are known to those skilled in the art. Examples include
methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, etc
(2) Substituted hydrocarbon groups; that is, groups cont~ining non-
hydrocarbon substituents which, in the context of this invention, do not alter the
predomin~ntly hydrocarbon character of the group. Those skilled in the art will
be aware of suitable substituents. Examples include halo, hydroxy, nitro, cyano,alkoxy, acyl, etc.
(3) Hetero groups; that is, groups which, while predominantly
hydrocarbon in character within the context of this invention, contain atoms other
than carbon in a chain or ring otherwise composed of carbon atoms. Suitable
hetero atoms will be apparent to those skilled in the art and include, for example,
nitrogen, oxygen and sulfur.
In general, no more than about three substituents or hetero atoms, and
preferably no more than one, will be present for each 10 carbon atoms in the
hydrocarbyl group.
Terms such as "alkyl-based," "aryl-based," and the like have meanings
analogous to the above with respect to alkyl groups, aryl groups and the like.
The term "hydrocarbon-based" has the same meaning and can be used
interchangeably with the term hydrocarbyl when referring to molecular groups
having a carbon atom attached directly to the remainder of a molecule.
The term "lower" as used herein in conjunction with terms such as
hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe such
groups which contain a total of up to 7 carbon atoms.
The term "oil-soluble" refers to a material that is soluble in mineral oil to
the extent of at least about one gram per liter at 25C.
(A) Acylated Amines.
The acylated amines (A) that are useful with the inventive automatic
tr~n~mission fluids are made by contacting (A)(I) a carboxylic acid acylating
~ 21 7~7
-35-
agent with (A)(II) a polyamine to provide an acylated amine characterized by a
base number in the range of about 45 to about 90, and in one embodiment about
45 to about 70. The term "base number" or "total base number (TBN)" as used
herein refers to the amount of acid (perchloric or hydrochloric) needed to
5 neutralize the product (A), excluding diluent oil and unreacted components,
expressed as KOH equivalents.
(A)(l) CarboxYlic Acid Ac~latin~ A~ents.
The acylating agents (A)(I) are well known in the art and have been found
10 to be useful as additives for lubricants and fuels and as intermediates for
preparing the same. See, for example, the following U.S. Patents which are
hereby incorporated by reference for their disclosures relating to carboxylic acid
acylating agents: 3,219,666; 3,272,746; 3,381,022; 3,254,025; 3,278,550;
3,288,714; 3,271,310; 3,373,111; 3,346,354; 3,272,743; 3,374,174; 3,307,928;
and 3,394,179.
Generally, these carboxylic acid acylating agents are prepared by reacting
an olefin polymer or chlorinated analog thereof with an unsaturated carboxylic
acid or derivative thereof such as acrylic acid, fumaric acid, maleic anhydride and
the like. Often they are polycarboxylic acylating agents such as hydrocarbyl-
substituted succinic acids and anhydrides. These acylating agents generally haveat least one hydrocarbyl substituent of at least about 8 carbon atoms, and in one
embodiment at least about 12 carbon atoms, and in one embodiment at least
about 20 carbon atoms, and in one embodiment at least about 30 carbon atoms,
and in one embodiment at least about 50 carbon atoms. Generally, this
substituent has an average of about 12 or about 20, typically about 30 or about
50 up to about 300 or about 500 carbon atoms; often it has an average of about
50 to about 250 carbon atoms.
The olefin monomers from which the olefin polymers are derived are
polymerizable olefins and monomers characterized by having one or more
ethylenic unsaturated group. They can be monoolefinic monomers such as
- 2 1 ~ 7
-36-
ethylene, propylene, butene-1, isobutene and octene-1 or polyolefinic monomers
(usually di-olefinic monomers such as butadiene-1,3 and isoprene). Usually thesemonomers are terminal olefins, that is, olefins characterized by the presence ofthe group >C=CH2. However, certain internal olefins can also serve as monomers
5 (these are sometimes referred to as medial olefins). When such medial olefin
monomers are used, they normally are employed in combination with terminal
olefins to produce olefin polymers which are interpolymers. Although the
hydrocarbyl-based substituents may also include aromatic groups (especially
phenyl groups and lower alkyl and/or lower alkoxy-substituted phenyl groups
10 such as para(tertiary butyl)-phenyl groups) and alicyclic groups such as would be
obtained from polymerizable cyclic olefins or alicyclic-substituted polymerizable
cyclic olefins. The olefin polymers are usually free from such groups.
Nevertheless, olefin polymers derived from such interpolymers of both 1,3-dienesand sly,enes such as butadiene-1,3 and styrene or para(tertiary butyl)styrene are
15 exceptions to this general rule.
Generally, the olefin polymers are homo- or interpolymers of terminal
hydrocarbyl olefins of about 2 to about 16 carbon atoms. A more typical class ofolefin polymers is selected from that group con~icting of homo- and
interpolymers of terminal olefins of 2 to 6 carbon atoms, especially those of 2 to
20 4 carbon atoms.
Specific examples of terminal and medial olefin monomers which can be
used to prepare the olefin polymers from which the hydrocarbyl substituents are
derived include ethylene, propylene, butene-l, butene-2, isobutene, pentene-l,
hexene-l, heptene-1, octene-1, nonene-1, decene-l, pentene-2, propylene
25 tetramer, diisobutylene, isobutylene trimer, butadiene- 1,2, butadiene- 1,3,
pentadiene-1,2, pentadiene-1,3, isoprene, hexadiene-1,5, 2-chlorobutadiene-1, 3,2-methylheptene-1, 3-cyclohexyl butene-l, 3,3-dimethylpentene-1,
styrenedivinylbenzene, vinyl~cet~te allyl alcohol, 1-methylvinyl~cet~te,
acrylonitrile, ethylacrylate, ethylvinylether and methylvinylketone. Of these, the
~_ 2 1 78037
purely hydrocarbyl monomers are more typical and the terminal olefin monomers
are especially typical.
Often the olefin polymers are poly(isobutenes) such as obtained by
polymerization of a C4 refinery stream having a butene content of about 35% to
about 75% by weight and an isobutene content of about 30% to about 60% by
weight in the presence of a Lewis acid catalyst such as ~luminum chloride or
boron trifluoride. These polyisobutenes usually contain predomin~ntly (that is,
greater than 80% of the total repeat units) isobutene repeat units of the
configuration
CH3
-CH2C-
CH3
Often the acylating agents (A)(I) are substituted succinic acids or
anhydrides which can be represented by the formulae
o
R-CHCOOH or R-CHC
CH2COOH
/ o
CH2C ~
wherein R is a hydrocarbyl group (eg., alkyl or alkenyl) of about 12 to 500
carbon atoms, and in one embodiment about 30 to about 500 carbon atoms, and
in one embodiment about 50 to about 500 carbon atoms.
These succinic acid acylating agents can be made by the reaction of maleic
anhydride, maleic acid, or fumaric acid with the afore-described olefin polymer,
2 1 78037
as is shown in the patents cited above. Generally, the reaction involves merely
heating the two reactions at a temperature of about 150C to about 200C.
Mixtures of the afore-said polymeric olefins, as well as mixtures of unsaturatedmono- and dicarboxylic acids can also be used.
In one embodiment the acylating agent (A)(I) is a substit~lted succinic acid
or anhydride, said substituted succinic acid or anhydride con~i~tinf~ of substitue.nt
groups and succinic groups wherein the substituent groups are derived from
polybutene in which at least about 50% of the total units derived from butenes is
derived from isobutylene. The polybutene has an Mn value of about 800 to
about 1200 and an Mw I Mn value of about 2 to about 3. The acids or anhydrides
are characterized by the presence within their structure of an average of about
0.9 to about 1.2 succinic groups for each equivalent weight of substituent
groups. For purposes of this invention, the number of equivalent weights of
substituent groups is the number corresponding to the quotient obtained Sy
dividing the Mn value of the polyalkene from which the substituent is derived
into the total weight of the substituent groups present in the
substituted succinic acid. Thus, if a substituted succinic acid is characterized by a
total weight of substituent group of 40,000 and the Mn value for the polyalkene
from which the substituent groups are derived is 2000, then that substit~lted
succinic acylating agent is characterized by a total of 20 (40,000/2000=20)
equivalent weights of substituent groups.
(A)(II) Polyamine.
The polyamine (A)(II) is selected from the group con~i~ting of (A)(II)(a)
a condensed polyamine derived from at least one hydroxy material and at least
one amine, (A)(II)(b) an alkylene polyamine bottoms product, or (A)(II)(c) a
condensed polyamine derived from at least one hydroxy material and at least one
alkylene polyamine bottoms product.
2 1 78037
-39-
~lydroxy Material Used in Makin~ Condensed PolYamines (A)(lI)(a)
and (A)(~I)(c).
The hydroxy material used in making (A)(II)(a) or (A)(II)(c) can be any
5 hydroxy material that will condense with the amine re~ct~nts ref~l-ed to aboveand discussed below. These hydroxy materials can be aliphatic, cycloaliphatic oraromatic alcohols. These alcohols can be monohydric or polyhydric.
The hydro~y materials include alkylene glycols and polyoxyalkylene
alcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols,
10 polyoxybutylene alcohols, and the like. These polyoxyalkylene alcohols
(sometimes called polyglycols) can contain up to about 150 oxyalkylene groups,
with the alkylene group cont~ining from about 2 to about 8 carbon atoms. Such
polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the
molecule termin~tes with an OH group. In order for such polyoxyalkylene
15 alcohols to be useful, there must be at least one such OH group. However, theren ~ining OH group can be esterified with a monobasic, aliphatic or aromatic
carboxylic acid of up to about 20 carbon atoms such as acetic acid, propionic
acid, oleic ac;d, stearic acid, benzoic acid, and the like. The monoethers of these
alkylene glycols and polyoxyalkylene glycols are also useful. These include the
20 monoaryl ethers, monoalkyl ethers, and monoaralkyl ethers of these alkylene
glycols and polyoxyalkylene glycols. This group of alcohols can be
reprcscnted by the formula
HO-(-R~ o^)pR2-oR3
wherein R' and R2 are independently alkylene groups of from about 2 to 8 carbon
atoms; and R3 is aryl (e.g., phenyl), lower alkoxy phenyl, or lower alkyl phenyl,
or lower alkyl (e.g., ethyl, propyl, terbutyl, pentyl, etc.); and aralkyl (e.g., benzyl,
phenylethyl, phenylpropyl, p-ethylphenylethyl, etc.); p is from zero to about
30 eight, preferably from about 2 to 4. Polyoxyalkylene glycols where the alkylene
`- 2 1 7ao37 -40-
groups are ethylene or propylene and p is at least two as well as the monoethersthereof as described above are useful.
The hydroxy materials that are useful include polyhydroxy aromatic
compounds, especially the polyhydric phenols and naphthols. These
S hydroxysubstituted aromatic compounds may contain other substituents in
addition to the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy,
alkylmercapto, nitro and the like. Usually, the hydroxy aromatic compound will
contain from 1 to about 4 hydroxy groups. The aromatic hydroxy compounds are
illustrated by the following specific examples: beta-naphthol, alpha-naphthol,
10 cresols, resorcinol, catechol, thymol, eugenol, p,p'-dihydroxy-biphenyl,
hydroquinone, pyrogallol, phloroglucinol, hexylresorcinol,4,4'-methylene-bis-
methylene-bis-phenol, alpha-decyl-beta- naphthol, the condçn~tion product of
heptylphenol with about 0.5 mole of formaldehyde, the contl~nc~tion product of
octylphenol with acetone, di(hydroxyphenyl)oxide, di-(hydroxyphenyl)sulfide,
15 and di(hydroxyphenyl)- disulfide.
Examples of monohydric alcohols which can be used include meth~nol,
ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol,
hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, beta-
phenylethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol, monomethyl
20 ether of ethylene glycol, monobutyl ether of ethylene.
Other specific alcohols that can be used are the ether alcohols and amino
alcohols including for example, the oxyalkylene-, oxyarylene-, ~mino~lkylene-
~and amino-arylene-substituted alcohols having one or more oxyalkylene,
aminoalkylene or amino-aryleneoxy-arylene groups. These alcohols are
25 exemplified by the Cellosolves, (products of Union Carbide identified as mono-
and dialkyl ethers of ethylene glycol and their derivatives), the Carbitols
(products of Union Carbide identified as mono- and dialkyl ethers of diethylene
glycol and their derivatives), mono-(heptylphenylo~propylene)-subs~ituted
glycerol, poly(styreneoxide), aminoethanol, di(hydroxyethyl)amine, N,N,N',N'-
30 tetrahydroxytrimethylenediamine, and the like.
21 7~û3~
-41-
In one embodiment, the polyhydric alcohols contain from 2 to about 10
hydroxy groups. These are illustrated, for example, by the alkylene glycols and
polyoxyalkylene glycols mentioned above such as ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene
glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols and
polyoxyalkylene glycols in which the alkylene groups contain from 2 to about 8
carbon atoms.
Useful alcohols also include those polyhydric alcohols cont~ining up to
about 12 carbon atoms, and especially those cont~ining from about 3 to about 10
carbon atoms. This class of alcohols includes glycerol, erythritol, pentaerythritol,
dipentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-
heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-
hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid,
2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol, digitalose, and
the like. Aliphatic alcohols cont~inin~. at least about 3 hydroxyl groups and up to
about 10 carbon atoms are useful.
Amino alcohols contemplated as suitable for use as the hydroxy
cont~ining reactant include those amino alcohols having two or more hydroxy
groups. Examples of suitable amino alcohols are the N-(hydroxy-lower
alkyl)amines and polyamines such as di-(2-hydroxyethyl)-amine,
tris(hydroxymethyl)amino methane (THAM), tri-(2-hydroxyethyl)amine, N,N,N'-
tri-(2-hydro~yethyl)ethylenetli~mine, N-(2-hydroxypropyl)-5-carbethoxy-2-
piperidone, and ethers thereof with aliphatic alcohols, especially lower alkanols,
N,N-di-(3-hydl o~y~ropyl)glycine, and the like. Also contemplated are other
poly-N-hydroxyalkyl-substituted alkylene polyamines wherein the alkylene
polyamine are as described above; especially those that contain 2 to 3 carbon
atoms in the alkylene radicals.
A group of alcohols representative of the above compounds can be
represented by the formula
(R)n-Y-(X)q (AOH)m
~ 21 7~0~7
-42-
wherein R is independently hydrogen or a hydrocarbyl, Y represents S, N, or O;
A and X each independently represent an alkylene group; n is 0, 1 or 2 dependentuponmandq,whereqisOorlandmisl,2,or3.
Polyoxyalkylene polyols which have two or three hydroxyl groups and
contain hydrophobic portions represented by the formula
-CHCH20-
R
wherein R' is a lower alkyl of up to 3 carbon atoms, and hydrophilic portions
cont~ining -CH2CH20- groups are useful. These polyols can be prepared by first
reacting a compound of the formula R2(0H)q where q is 2-3 and R2 is
hydrocarbyl with a terminal alkylene oxide of the formula
R-CH-CH2
\l
0
and then reacting that product with ethylene oxide. R2(0H)q can also be, for
example, trimethylolpropane, trimethylolethane, ethylene glycol, trimethylene
glycol, tetramethylene glycol, tri-(beta-hydroxypropyl)amine, 1,4-(2-
hydroxyethyl)cyclohexane, tris-(hydroxymethyl)amino methane, 2-amino-2-
methyl- 1,3 -propanediol, N,N,N' ,N'-tetrakis(2-hydroxypropyl)- ethylene diamine,N,N,N',N'-tetrakis(2-hydroxyethyl)-ethylene diamine, resorcinol, and the like.
The foregoing described R2(0H)q polyols may also be used alone as the hydroxy
cont~ining react~nt
Other hydroxy-containing reactants that can be used are hydroxyalkyl,
hydroxy alkyl oxyalkyl and hydroxy aryl sulfides of the formula
Sf(ROH)2f
21 78~7
-43 -
wherein f is 1 or 2, and R is an alkyl of 1 to about 10 carbon atoms or an alkyloxyalkyl where the alkyl is 1 to about 10 carbon atoms and in one embodiment 2
to about 4 carbon atoms, and aryl is at least 6 carbon atoms. Examples include
5 2,2'-thiodiethanol and 2,2'-thiodipropanol.
Amines Useful in ~lakin~ the Polyamines (A)(II)(a).
The amines usefi l in making the polyamines (A)(II)(a) include primary
amines and secondary amines. These amines are characterized by the presence
within their structure of at least one H-N< group and/or at least one -NH2 group.
10 These amines can be monoamines or polyamines, with the polyamines being
.eîel~d. Mixtures oftwo or more amines can be used.
The amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic,
including aliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic,
aliphatic-substituted heterocyclic, cycloaliphatic-substitllted aliphatic,
15 cycloaliphatic substituted aromatic, cycloaliphatic-substituted heterocyclic,aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic, aromatic-
substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic-
substituted cycloaliphatic and heterocyclic-substituted aromatic amines~ These
amines may be saturated or unsaturated. If unsaturated, the amine is preferably
20 free from acetylenic unsaturation. The amines may also contain non-hydrocarbon
substituents or groups as long as these groups do not significantly interfere with
the reaction of the amines with the hydroxy materials used in making the
condensed polyamines (A)(II)(a). Such non-hydrocarbon substit~lents or groups
include lower alkoxy, lower alkyl, mercapto, nitro, and inte~upliilg groups such25 as -O- and -S- (e.g., as in such groups as -CH2CH2-X-CH2CH2- where X is -O-
or -S-).
With the exception of the branched polyalkylene poly~mines, the
polyoxyalkylene polyamines and the high molecular weight hydrocarbyl-
substituted amines described more fully hereinafter, the amines used in this
2 1 7~Q~
-44-
invention ordinarily contain less than about 40 carbon atoms in total and usually
not more than about 20 carbon atoms in total.
Aliphatic monoamines include mono-aliphatic and di-aliphatic-substituted
amines wherein the aliphatic groups can be saturated or unsaturated and straight5 or branched chain. Thus, they are primary or secondary aliphatic amines. Such
amines include, for example, mono- and di-alkyl-substituted amines, mono- and
di-alkenyl-substituted amines, and amines having one N-alkenyl substituent and
one N-alkyl substituent, and the like. The total number of carbon atoms in thesealiphatic monoamines preferably does not exceed about 40 and usually does not
10 exceed about 20 carbon atoms. Specific examples of such mono~mines include
ethylamine, di-ethyl amine, n-butylamine, di-n-butylamine, allylamine,
isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine,
oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine, and the like.
Examples of cycloaliphatic-substituted aliphatic amines, aromatic-substituted
15 aliphatic amines, and heterocyclic-substituted aliphatic amines, include 2-
(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and 3-(furylpropyl)
amine.
Examples of useful polyamines include N-aminopropyl-cyclohexyl amine,
N-N'-di-n-butyl-para-phenylene diamine, bis-(para-aminophenyl)methane, 1,4-
20 diaminocyclohexane, and the like.
Heterocyclic monoamines and polyamines can be used. As used herein,the terminology Nheterocyclic mono- and polyamine(s)" is intended to describe
those heterocyclic amines cont~ining at least one primary or secondary amino
group and at least one nitrogen as a heteroatom in the heterocyclic ring. These
25 heterocyclic amines can be saturated or unsaturated and can contain various
substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or
aralkyl substituents. Generally, the total number of carbon atoms in the
substituents will not exceed about 20. Heterocyclic amines can contain more
than one nitrogen heteroatom. The 5- and 6-membered heterocyclic rings are
~0 preferred.
21 ~81~37
-45 -
Among the suitable heterocyclics are aziridines, azetidines, azolidines,
tetra- and di-hydropyridines, pyrroles, indoles, piperadines, imidazoles, di- and
tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines,
thiomorpholines, N-aminoalkyl-morpholines, N-arninoalkylthiomorpholines, N-
aminoalkyl-piperazines, N,N'-di-aminoalkylpiperazines, azepines, azocines,
azonines, azecines and tetra-, di- and perhydroderivatives of each of the above
and mixtures of two or more of these heterocyclic amines. Preferred heterocyclicamines are the saturated 5- and 6-membered heterocyclic amines cont~ining only
nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines,
piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.
Piperidine, amino alkyl - substituted piperidines, piperazine, aminoalkyl-
substituted piperazines, morpholine, aminoalkyl-substituted morpholines,
pyrrolidine, and aminoalkyl-substituted pyrrolidines, are useful. Usually the
aminoalkyl substituents are substituted on a nitrogen atom forming part of the
hetero ring. Specific examples of such heterocyclic amines include N-
aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-di-
aminoethylpiperazine.
Also suitable as amines are the aminosulfonic acids and derivatives thereof
corresponding to the formula:
12 3 1
(R R N ~R (S R)y
Il
wherein R is OH, NH2, ONH4, etc.; R3 is a polyvalent organic group having a
valence equal to x + y; Rl and R2 are each independently hydrogen, hydrocarbyl
or substituted hydrocarbyl with the proviso that at least one of Rl and R2 is
25 hydrogen; x and y are each integers equal to or greater than one. Each
~ 1 78Q37
-46-
aminosulfonic reactant is characterized by at least one HN< or H2N- group and atleast one
o
-~-R
Il
o
group. These sulfonic acids can be aliphatic, cycloaliphatic or aromatic
5 aminosulfonic acids and the corresponding functional derivatives of the sulfo
group. Specifically, the aminosulfonic acids can be aromatic aminosulfonic acids,
that is, where R3 is a polyvalent aromatic group such as phenylene where at least
one
S R
group is attached directly to a nuclear carbon atom of the aromatic group. The
aminosulfonic acid may also be a mono-amino aliphatic sulfonic acid; that is, anacid where x is one and R3 is a polyvalent aliphatic group such as ethylene,
propylene, trimethylene, and 2-methylene propylene. Other suitable
15 aminosulfonic acids and derivatives thereof useful as amines in this invention are
disclosed in U.S. Patents 3,029,250; 3,367,864; and 3,926,820; which are
incorporated herein by reference.
The high molecular weight hydrocarbyl polyamines which can be used as
amines in this invention are generally prepared by reacting a chlorinated
20 polyolefin having a molecular weight of at least about 400 with ammonia or anamine. The amines that can be used are known in the art and described, for
example, in U.S. Patents 3,275,554 and 3,438,757, both of which are
~ 1 78037
`
-47-
incorporated herein by reference. These amines must possess at least one primaryor secondary amlno group.
Another group of amines suitable for use in this invention are branched
polyalkylene polyamines. The branched polyalkylene polyamines are polyalkylene
S polyamines wherein the branched group is a side chain cont~ining on the average
at least one nitrogen-bonded aminoalkylene
H
I
(i.e., NH2-R-N-RX-)
group per nine amino units present on the main chain; for example, 1-4 of such
branched chains per nine units on the main chain, but preferably one side chain
unit per nine main chain units. Thus, these polyamines contain at least three
primary amino groups and at least one tertiary amino group. U.S. Patents
3,200,106 and 3,259,578 are incorporated herein by reference for their
disclosures relative to said polyamines.
Suitable amines also include polyoxyalkylene polyamines, e.g.,
polyoxyalkylene diamines and polyoxyalkylene triamines, having average
molecular weights ranging from about 200 to about 4000, and in one embodiment
from about 400 to 2000. Examples of these polyoxyalkylene polyamines include
those amines represented by the formula:
NH2Alkylene-(-O-Alkylene-)mNH2
wherein m has a value of from about 3 to about 70, and in one embodiment from
about 10 to about 35; and the formula:
R-[Alkylene-(-o-Alkylene-)nNH2)
2 ~ 78037
-48-
wherein n is a number in the range of from 1 to about 40, with the proviso that
the sum of all of the n's is from about 3 to about 70 and generally from about 6 to
about 35, and R is a polyvalent saturated hydrocarbyl group of up to about 10
carbon atoms having a valence of from about 3 to about 6. The alkylene groups
5 may be straight or branched chains and contain from 1 to about 7 carbon atoms,and usually from 1 to about 4 carbon atoms. The various alkylene groups present
within the above formulae may be the same or different.
Useful polyoxyalkylene polyamines include the polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines having average
molecular weights ranging from about 200 to about 2000. The polyoxyalkylene
polyamines are commercially available from the Jefferson Chemical Colllpar~
Inc. under the trade name "Jeff~mine." U.S. Patents 3,804,763 and 3,948,800 are
incorporated herein by reference for their disclosure of such polyoxyalkylene
polyamines.
Useful amines are the alkylene polyamines conforming to the formula:
H-N-(Alkylene-N)nR
R R
wherein n is from 1 to about 10; each R is independently a hydrogen atom, a
20 hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to
about 700 carbon atoms, and in one embodiment up to about 100 carbon atoms,
and in one embodiment up to about 30 carbon atoms; and the "Alkylene" group
has from about 1 to about 10 carbon atoms with the preferred alkylene being
ethylene or propylene. Useful are the alkylene polyamines wherein each R is
25 hydrogen with the ethylene polyamines, and mixtures of ethylene polyamines
being particularly preferred. Usually n will have an average value of from about 2
to about 7. Such alkylene polyamines include methylene polyamines, ethylene
polyamines, butylene polyamines, propylene polyamines, pentylene polyamines,
hexylene polyamines, heptylene polyamines, etc. The higher homologs of such
30 amines and related aminoalkyl-substituted piperazines are also included.
2 1 78037
-49-
Alkylene polyamines that are useful include ethylene diamine, triethylene
tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine,
decamethylene diamine, octamethylene diarnine, di(heptamethylene) triamine,
tripropylene tetramine, tetraethylene pent~mine, trimethylene diamine,
5 pentaethylene hexamine, di(trimethylene) triamine, N-(2-aminoethyl) piperazine,
1,4-bis(2-amino ethyl) piperazine, and the like. Higher homologs as are obtainedby condensing two or more of the above-illustrated alkylene amines are useful asamines in this invention as are mixtures of two or more of any of the
aforedescribed polyamines.
Ethylene polyamines, such as those mentioned above, are described in
detail under the heading "Diamines and Higher Amines" in The Encyclopedia of
Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages 27-
39, Interscience Publishers, Division of John Wiley and Sons, 1965, these pages
being incorporated herein by reference. Such compounds are prepared most
15 conveniently by the reaction of an alkylene chloride with ammonia or by reaction
of an ethylene imine with a ringopening reagent such as ammonia, etc. These
reactions result in the production of the somewhat complex mixtures of alkylene
polyamines, including cyclic condensation products such as piperazines.
A useful class of polyamines that can be used are those represented by the
20 formula
H-N-(Z-NR')X-R
R
in which each R is hydrogen or a hydrocarbyl group; each R' is independently
25 hydrogen, alkyl, or NH2R"(NR")y~ where each R" is independently an alkylene
group of 1 to about 10 carbon atoms and y is a number in the range of from 1 to
about 6; each Z is independently an alkylene group of 1 to about 10 carbon
atoms, a heterocyclic nitrogen cont~inin~. cycloalkylene or an oxyalkylene groupof 1 to about 10 carbon atoms and x is a number in the range of from 1 to about
30 10.
2 1 78~3J
so
Polvamine Bottoms Useful as Polvamines (A)(II)(b) or in Makin~
Condensed Polvamin es (A) (ll) (c).
The polyamine bottoms that can be used as either the polyamines
(A)(II)(b) or in making the condensed polyamines (A)(II)(c) are polyamine
S mixtures resulting from stripping of the alkylene polyamine mixtures ~liscllssed
above. Lower molecular weight polyamines and volatile con~min~tes are
removed from an alkylene polyamine mixture to leave as residue what is often
termed "polyamine bottoms." In general, alkylene polyamine bottoms can be
characterized as having less than 2%, usually less than 1% by weight material
10 boiling below about 200C. In the instance of ethylene polyamine bottoms, thebottoms contain less than about 2% by weight total diethylene triamine (DETA)
or triethylene tetramine (TETA). A typical sample of such ethylene polyamine
bottoms obtained from the Dow Chemical Company of Freeport, Texas
designated "E-100" showed a specific gravity at 15.6C of 1.0168, a percent
nitrogen by weight of 33.15 and a viscosity at 40C of 121 cen~istQkes. Gas
chromatography analysis of such a sample showed it to contain about 0.93%
"Light Ends" (DETA), 0.72% TETA, 21.74% tetraethylene pçnt~mine and
76.61% pentaethylene hexamine and higher (by weight). These alkylene
polyamine bottoms include cyclic condensation products such as piperazine and
higher analogs of diethylene triamine, triethylene tetramine and the like.
Process for Makin~ the Condensed PolYAmines (A)(II)(a) and
(A)(II)(c).
The reaction between the hydroxy material and the amine to form the
condensed polyamines (A)(II)(a) and (A)(II)(c) requires the presence of an acid
2S catalyst. The catalysts that are useful include mineral acids (mono, di- and
polybasic acids) such as sulfuric acid and phosphoric acid; organo phosphorus
acids and organo sulfonic acids such as RP(O)(OH)2 and RSO3H, wherein R is
hydrocarbyl; alkali metal partial salts of H3PO4 and H2SO4, such as NaHSO4,
LiHSO4, KHSO4, NaH2PO4, LiH2PO4 and KH2PO4; alkaline earth metal partial
salts of H3PO4 and H2SO4, such as CaHPO4, CaS04 and Mg HPO4; also Al203
21 7803J
and Zeolites. Phosphoric acid is useful because of its commercial availability and
ease of handling. Also useful as catalysts for this invention are materials which
generate acids when treated in the reaction mixture, e.g., triphenylphosphite.
The reaction is run at an elevated temperature which, depending upon the
particular reactants, can range from about 60C to about 265C. Most reactions,
however, are run in the range of about 220C to about 250C. The reaction may
be run at atmospheric pressure or optionally at a reduced pressure depending
upon the particular reactants. The degree of condensation of the resl-lt~nt
polyamine is limited only to the extent necessary to prevent the formation of solid
products under reaction conditions. The control of the degree of condensation ofthe product is normally accomplished by limiting the amount of the condensing
agent, i.e., the hydroxy material, charged to the reaction medium. In one
embodiment, the condensed polyamines are pourable at room temperature and
have viscosities which range from about 100% greater than the viscosity of the
amine reactant to about 6000% greater than the viscosity of the amine re~ct~nt
In one embodiment, the condensed polyamines have viscosities which range from
about 50% to about 1000% greater than the viscosity of the amine react~nt In
one embodiment, the viscosity of the condensed polyamines ranges from about
50 cSt to about 200 cSt at 100C.
Process for M~kin~ the Acvlated Amine (A).
The carboxylic acid acylating agents (A)(I) can be reacted with the
polyamines (A)(II) according to conventional amide, imide or amidene forming
techniques to form the acylated amines (A). This normally involves heating the
acylating agent (A) with the polyamine (A)(II), optionally in the presence of a
normally liquid, substantially inert, organic liquid solvent/diluent. Tempe-alllres
of at least about 30C up to the decomposition temperature of the reaction
component and/or product having the lowest such temperature can be used. This
temperature usually is in the range of about 80C to about 250C.
The relative proportions of the acylating agent (A)(I) and the polyamine
(A)(II) to be used in the above process are such that at least about one-half of a
21 78037
stoichiometrically equivalent amount of the polyamine (A)(II) is used for each
equivalent of the acylating agent (A)(I) used. In this regard it will be noted that
the equivalent weight of the polyamine (A)(II) is based upon the number of the
nitrogen-cont~ining groups defined by the structural configuration
-N-H
Similarly the equivalent weight of the acylating agent (A)(I) is based upon the
number of the acid-producing groups defined by the structural configuration
o
-C-X
15 Thus, ethylene diamine has two equivalents per mole; amino guanidine has fourequivalents per mole; a succinic acid or ester has two equivalents per mole, etc.
The upper limit of the useful amount of the polyamine (A)(II) appears to be
about two moles for each equivalent of the acylating agent (A)(I) used. Such
amount is required, for instance, in the formation of products having
20 predomin~ntly amidine linkages. Beyond this limit, the excess amount of the
polyamine (A)(II) appears not to take part in the reaction. On the other hand, the
lower limit of about one-half equivalent of the polyamine (A)(II) used for each
equivalent of the acylating agent (A)(I) is based upon the stoichiometry for theformation of products having predomin~ntly imide linkages. In most in~t~nces,
25 the amount of the polyamine (A)(II) is approxil,lately one equivalent for each
equivalent of the acylating agent (A)(I) used. In one embodiment, the acylated
amines (A) are prepared in the same manner as the polyamines (A)(II) of the
present invention. That is, they are prepared by the acid catalyzed condensationreaction of at least one carboxylic acylating agent (A)(I) with at least one
30 polyamine (A)(II). The catalysts previously described with respect to the
polyamines (A)(II) are useful in this reaction. The acylated amines (A) generally
21 7~37
`
have a total base number (TBN) in the range of about 45 to about 90, and in one
embodiment about 55 to about 80. The following examples are illustrative of the
preparation of acylated amines (A) that are usefi~l with this invention. In the
following example, as well as throughout the specification and in the claims,
S unless otherwise indicated, all parts and percentages are by weight, all
temperatures are in degrees Celsius, and all pressures are at or near atmospheric.
Example A-1
Part I
A mixture of 76.4 pnrts by weight of HPA-X (a product of Union
Carbide identifed as a polyamine bottoms product having a nitrogen
content of 31.5% by weight and an average base number of 1180)
and 46. 7 parts by veight of THAM (trishydroxymethyl
aminomethnne) are heated at a temperature of 220C under
condensation reaction conditions in the presence of 1.25 parts by
weight of an 85% by weight phosphoric acid aqueous solution to
form a condensed polyaminG 1. 7 parffs by weight a 50% aqueous
solution of NaOH are then added to the reaction mixture to
neutralize the phosphoric acid. The re~ulting product is a con(~en~e~
polyamine having the following properties: viscosity at 40C of 6500
cSt; viscosity at 100C of 90 cSt; total base number of 730; and
nitrogen content of 27% by weight.
Paff n
A mixture of 1000 parts by weight of polyisobutenyl
(Mn=lOOOJ succinic anhydride and 400 parffs by weight of diluent
oil are charged to a reactor while mixing under a N2 purgG The
batch temperature is adjusted to 88C. 152 parts by weight of the
condensed polyamine from Part I are charged to the reactor while
maintaining the reactor temperature at 88-93C. The molar ratio
of acid to nitrogen is I COOH: I.55N. The batch is mixedfor two
hours at 82-96C, then heated to 152C over 5.5 hours. The Nt
2 1 78037
-54-
purge is discontinued and submerged N2 blowing is begun. The
batch is b1Own to a water content of 0.30% by weight or less at 149-
154C, cooled to 138-149C and filtered. Diluent oU is added to
provide an oil content of 40% by weigkt. The r~sultil g product has
S a nitrogen content of 2.15% by weight, a viscosity at 100C of 210
cSt, and a total base number of 48.
Exnmple A-2
A mix~ure of 108 parts by weight of a polyamine mixture (15%
by weight diethylene triamine and 85% by weight polyamine bottoms)
and 698 parts by weight dilt~ent oil is charged to a reactor. 1000 parts
by weight of polyisobute~yl (Mn=1000) succinic anhydride are
charged to ~he reactor under a N2 purge while maintaining the batch
tempera~ure a~ 110-121C. The molar ratio of acid to nitrogen is 1
COOH: I.5N. After neu~ralization submerged N2 blowing is begun.
The batch is heated to 143-149C, and then filtered. Diluent oil is
added to provide an oil content of 40% by weight. The resulting
product has a ni~rogen content of 2. 0% by weight, a viscosity at 100C
of 135-155 cSt, and a totnl base number of 55.
(B) Boron ComPound.
The boron compound can be an inorganic or an organic compound. The
inorganic compounds include the boron acids, anhydrides, oxides and halides.
The organic boron compounds include the boron amides and esters. Also
included are the borated acylated amines of (A) as well other borated acylated
amines and borated dispersants, boràted epoxides and the borated fatty acid
esters of glycerol.
The boron compounds that are useful include boron oxide, boron oxide
hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride,boron acids such as boronic acid (i.e., alkyl-B(OH)2 or aryl-B(OH)2), boric acid(i.e., H3BO3), tetraboric acid (i.e., H2B407), metaboric acid (i.e., HBO2), boron
anhydrides, boron amides and various esters of such boron acids. Complexes of
~ 2 ~ 7803~
boron trihalide with ethers, organic acids, inorganic acids, or hydrocarbons canbe used. Examples of such complexes include boron-trifluoride-triethyl ester,
boron trifluoride-phosphoric acid, boron trichloride-chloroacetic acid, boron
tribromide-dioxane, and boron trifluoride methyl ethyl ether.
Specific examples of boronic acids include methyl boronic acid, phenyl-
boronic acid, cyclohexyl boronic acid, p-heptylphenyl boronic acid and dodecyl
boronic acid.
The boron acid esters include mono-, di-, and tri-organic esters of boric
acid with alcohols or phenols such as, e.g., methanol, ethanol, isopropanol,
cyclohexanol, cyclopentanol, I-octanol, 2-octanol, dodecanol, behenyl alcohol,
oleyl alcohol, stearyl alcohol, benzyl alcohol, 2-butyl cyclohexanol, ethylene
glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, 1,2-
cyclohexanediol, 1,3-octanediol, glycerol, pentaerythritol diethylene glycol,
carbitol, Cellosolve, triethylene glycol, tripropylene glycol, phenol, naphthol, p-
butylphenol, o,p-diheptyl phenol, n-cyclohexylphenol, 2,2-bis-(p-hydroxyphenyl)-propane, polyisobutene (molecular weight of 1500)-substituted phenol, ethylene
chlorohydrin, o-chlorophenol, m-nitrophenol, 6-bromooctanol, and 7-keto-
decanol. Lower alcohols, 1,2-glycols, and 1-3-glycols, i.e., those having less
than about 8 carbon atoms are especially useful for preparing the boric acid
esters for the purpose of this invention.
Methods for preparing the esters of boron acid are known and disclosed in
the art (such as "Chemical Reviews," pp. 959-1064, Vol. 56). Thus, one method
involves the reaction of boron trichloride with 3 moles of an alcohol or a phenol
to result in a tri-organic borate. Another method involves the reaction of boricoxide with an alcohol or a phenol. Another method involves the direct
esterification of tetra boric acid with 3 moles of an alcohol or a phenol. Stillanother method involves the direct esterification of boric acid with a glycol toform, e.g., a cyclic alkylene borate.
2 ~ 78Q37
-56-
Borated Acylated Amines.
The borated acylated amines can be prepared by first reacting a carboxylic
acid acylating agent with at least about one-half equivalent, per equivalent of
carboxylic acid acylating agent, of an amine cont~ining at least one hydrogen
5 attached to a nitrogen group. The acylated amine obtained in this manner is
usually a complex mixture of acylated amines. The acylated amine is then
bor,ated by reacting it with a boron compound of the type described above,
including the boron trioxides, boron halides. boron acids, boron amides, and
esters of boron acids.
The acylated amines that can be used are described above under the
subtitle "(A) Acylated Aminesn. Additional acylated amines that can be used are
described in the following U.S. patents:
3,087,936 3,341,542 3,630,904
3,172,892 3,346,493 3,632,511
3,215,707 3,444,170 3,787,374
3,254,025 3,454,607 4,234,435
3,272,746 3,541,012
3,316,177
The above U.S. patents are eApressly incorporated herein by reference for their
teaching of the preparation of acylated amines that are useful herein.
The amount of boron compound reacted with the acylated amine
25 intermediate generally is sufficient to provide from about 0.1 atomic proportion
of boron for each mole of the acylated amine up to about 10 atomic proportions
of boron for each atomic proportion of nitrogen of said acylated amine. More
generally the amount of boron compound present is sufficient to provide from
about 0.5 atomic proportion of boron for each mole of the acylated amine to
` 2178~37
-57-
about 2 atomic proportions of boron for each atomic proportion of nitrogen
used.
The reaction of the acylated amine with the boron compound can be
effected simply by mixing the re~ct~nts at the desired temperature. The use of an
S inert solvent is optional although it is o~en desirable, especially when a highly
viscous or solid reactant is present in the reaction mixture. The inert solvent may
be a hydrocarbon such as benzene, toluene, naphtha, cyclohexane, n-h~Y~n~, or
mineral oil. The temperature of the reaction may be varied within wide ranges.
Ordinarily it is preferably between about 50C and about 250C. In some
instances it may be 25C or even lower. The upper limit of the temperature is the
decomposition point of the particular reaction mixture and/or product.
The reaction is usually complete within a short period such as 0.5 to 6
hours. A~er the reaction is complete, the product may be dissolved in the solvent
and the resulting solution purified by centrifiJgation or filtration if it appears to be
hazy or contain insoluble substances. Ordinarily the product is sufficiently pure
so that fi~rther purification is unnecessary or optional.
The above described dispersants may be post treated with such reagents
as carbon disulfide to give a sul~unzed dispersant. This reaction type is pre~nted
in U.S. Patent 3,200,107 to LeSuer. An example of the preparation of a
sulfilrized succan dispersant is given below:
EXAMPLE 1
To a mixture of 1 750 grams of a mineral oil and 3500 grams
(6 5 equivalen~s) of a polyisobutene-substituJed succinic ankydride
having an acid number of 104 prepared by the reaction of maleic
anhydride with a chlorinated polyisobutene having a molecular
weight of 1000 and a chlorine content of 4 5% there is added at
70C-100G 946 grams (25 9 equivalents) of triethylene tetramine.
The reaction is exothermic The mixture is heated at 160C-1 70Cfor
12 hours vhile nitrogen is passed through the mixture, whereupon
59 cc of water is col~ected as ~he distilla~e The mixture is diluted
21 78037
-58-
wi~h 1165 grams of mineral oil and fltered. The fltrate is found to
have a nitrogerl content of 4.12%. The 6000 grams of the above
acylated product there is added 608 grams (16 equivalents) of carbon
disu~fde at 25-50C ~hroughout a period of 2 hours The mixture is
heated at 60-73Cfor 3 hours and then at 68-85C/7mn~ Hgfor S.5
hours. The residue is f iltered at 85C and the f Itrate is fol~nd to have
a nitrogen content of 4.45% and a sulfur content of 4.8%.
Dispersants can also be classified Mannich base dispersants. These are
reaction products between alkylphenols in which the alkyl group contains at least
about 30 carbon atoms with lower aliphatic aldehydes (especially formal dehydes)and amines. The preferred amines are polyalkylene polyamines. The dispersants
are well known in the art and are described in U.S. Patents 3,275,554, 3,454,555;
3,438,757 and 3,565,804 which are herein incorporated by reference for material
to do with Mannich dispersants.
The base oils of lubricating viscosity of utility in this invention are natural
oils from plants, animals and mineral lubricating oils such as liquid petroleum oils
and solvent treated or acid treated mineral lubricating oils of the parafinic,
naphtenic or mixed napthenic-parafinic types. Oils of lubricating viscosity fromcoal and shale are also useful.
The synthetic lubricating oils useful herein include hydrocarbon oils and
halo-substituted hydrocarbon oils such as polymerized and interpolymerized
olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers,
chlorinated polybutylenes, etc.); poly(l-hexenes), poly(l-octenes), poly(l-
decenes), etc. and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.);
polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated
diphenyl esters and alkylated diphenyl sulfides and the derivatives, analogs andhomologs thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof where
the terminal hydroxyl groups have been modified by esterification, etherification,
~1 78û37
sg
etc., constitute another class of known synthetic lubricating oils that can be used.
These are exemplified by the oils prepared through polymerization of ethylene
oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene
polymers (e.g., methyl polyisopropylene glycol ether having an average molecularS weight of about 1000, diphenyl ether of polyethylene glycol having a molecularweight of about 500-1000, diphenyl ether of polypropylene glycol having a
molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters
thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the
Cl30xo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating, oils that can be used
comprises the esters of dicraboxylic acids (e.g., phthalic acid, succinic acid, alkyl
succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid,sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkenyl
malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol,
dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol
monoether, propylene glycol, etc.). Specific examples of these esters include
dibutyl adipate, di(2-ethylhexyl)-sebasate, di-n-hexyl fumarate, dioctyl sebacate,
diisooctyl a_elate, diisodecyl~7el~te, dioctyl phthalate, didecyl phth~l~te,
dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complexester formed by reacting one mole of sebacic acid with two moles of
tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from C5 to C~2
monocarboxylic acids and polyols and polyol ethers such as neopentyl glycl,
trimethylol propane, pentaerythritol, dipentaerythriotol, tripentaerythriotol, etc.
Silicon-based oils such as the plyalkyl-, polyaryl- polyalkoxy- or
polyaryloxy silane oils and silicate oils comprise another useful class of synthetic
lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-
ethylhexyl)silicate, tetra-(4-methyl hexyl)silicate, tetra-(p-tert-
butylphenyl)silicate, hexyl(4-methyl-2-pentoxy)-disiloxane,
poly(methyl)siloxanes, poly(methylphenyl)-siloxanes, etc.). Other synthetic
2 1 ~3~
-60-
lubricating oils include liquid esters of phosphorus-containing acids (e.g.,
tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,
etc.), polymeric tetrahydrofurans and the like.
Polyolefin oligomers are typically formed by the polymerization reaction
S of alpha-olefins. Nonalpha-olefins may be oligomerized to give a synthetic oil
within the present invention, however, the reactivity and availability of alpha-olefins at low cost dictates their selection as the source of the oligomer.
The polyolefin oligomer synthetic lubricating oils of interest in the present
invention include hydrocarbon oils and halo-substituted hydrocarbon oils such asare obtained as the polymerized and interpolymerized olefins, e.g., oligomers,
include the polybutylenes, polypropylenes, propylene-isobutylene copolymers,
chlorinated polybutylenes, poly(l-hexenes), poly(1-octenes), poly(1-decenes),
similar materials and mixtures thereo
Typically, the oligomer is obtained from a monomer cont~ining from
lS about 6 to 18 carbon atoms, preferably from about 8 carbon atoms to about 12
carbon atoms. Most preferably, the monomer used to form the oligomer is
decene, and preferably 1-decene. The nomenclature alpha-olefin is a trivial nameand the IUPAC nomenclature of a 1-ene compound may be considered to have
the same meaning within the present invention.
While it is not essential that the oligomer be formed from an alpha-olefin,
such is desirable. The reason for forming the oligomer from an alpha-olefin is that
branching will naturally occur at the points where the olefin monomers are joined
together and any additional branching within the backbone of the olefin can
provide too high a viscosity of the end oil. It is also desirable that the polymer
formed from the alpha olefin be hydrogenated. The hydrogenation is conducted
according to known practices. By hydrogenating the polymer free radial attack
on the allyic carbons remaining after polymerication is minimized.
The molecular weight of the oligomer is typically averages from about
250 to about 1400, conveniently from about 280 to about 1200 preferably from
about 300 to about 1100 and most preferably about 340 to about 520. The choice
21 78037
-
-61-
of molecular weight of the oligomer is largely dependent upon whether a
viscosity improver is included within the formulation. That is, the polyolefin
oligomer, may require either a thickening or a thinnin~ effect to ensure that the
proper lubricating viscosities are m~int~ined under extreme heat and cold
5 conditions.
The table below gives examples of preferred compositions of blended
ATF's containing the present invention. Percents given are in weight percent of
each component based on weight of the ATF's. The blended ATF usually
comprises roughly about 80 percent by weight oil of lubricating viscosity and 20 percent by weight additive package.
Component Ranges
Oil of Lubricating Viscosity Majority
45-90%
Alkoxylated fatty amines 0.05-8%
Other friction modifiers, each 0.01-4%
Antioxidants up to 12%
Overbased metal organic acid up to 20%
Dispersants up to 20%
Viscosity Index Improver and/or up to 40%
dispersant-viscosity modifier
Extreme Pressure Agent up to 5%
Seal Swell up to 5%
85% phosphoric acid up to 3%
